Silicone skeleton-containing polymer compound, chemically amplified negative resist composition, photo-curable dry film and method for producing same, patterning process, layered product, substrate, and semiconductor apparatus

ABSTRACT

The present invention provides a silicone skeleton-containing polymer compound containing a repeating unit shown by the general formula (1). There can be provided a silicone skeleton-containing polymer compound suitable used as a base resin of a chemically amplified negative resist composition that can remedy the problem of delamination generated on a metal wiring such as Cu and Al, an electrode, and a substrate, especially on a substrate such as SiN, and can form a fine pattern without generating a scum and a footing profile in the pattern bottom and on the substrate.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a silicone skeleton-containing polymercompound, a chemically amplified negative resist composition using thesilicone skeleton-containing polymer compound, a photo-curable dry filmproduced by using the chemically amplified negative resist compositionand a method for producing the same, a patterning process using thechemically amplified negative resist composition or the photo-curabledry film, a layered product having the photo-curable dry film laminatedon a substrate, a substrate obtained by the patterning process, and asemiconductor apparatus having a cured film obtained by the patterningprocess.

Description of the Related Art

In accordance with the progress of various electronic devices includinga personal computer, a digital camera, and a mobile phone towarddownsizing and higher performance, requirements are rapidly increasingfor further downsizing, thinning, and higher density in a semiconductordevice. Accordingly, it is desired to develop a photosensitiveinsulation material that can accommodate not only an increase in surfacearea of a substrate for the sake of higher productivity, but alsostructures having fine concavity and convexity with a high aspect ratioon a substrate, in high density mounting technologies including a chipsize package or a chip scale package (CSP) and a three-dimensionallamination.

As to the above-mentioned photosensitive insulation material, there hasbeen proposed a photo-curable resin composition (Patent Document 1) thatcan be applied so as to give a wide range of film thickness by a spincoating method commonly used in the semiconductor device fabrication,can be processed into a fine pattern using a wide range of wavelength,and can be post-cured at low temperature into a top coat havingexcellent flexibility, heat resistance, electric characteristics,adhesiveness, reliability, and chemical resistance to protect electricand electronic parts. The spin coating method has an advantage that afilm can be readily formed on a substrate.

The above-mentioned photo-curable resin composition for providing a topcoat to protect electric and electronic parts is used with a filmthickness of 1 to 100 μm on a substrate. However, there is a practicallimit in the photo-curable resin composition because when the filmthickness exceeds about 30 μm, its viscosity becomes too high to form afilm on a substrate by the spin coating method.

Also, when the photo-curable resin composition is applied onto asubstrate having an uneven surface by spin coating, it is difficult toform a uniform layer on the substrate. Because of this, thephoto-curable resin layer tends to generate voids on the uneven part ofthe substrate, and thus, further improvements in planarity and stepcoverage have been desired. As the alternative coating method in placeof the spin coating method, a spray coating method has been proposed(Patent Document 2). However, in principle, this method tends to readilycause defects such as height difference due to unevenness of thesubstrate, film loss at pattern edge, and a pinhole in recess bottom;and thus, the problems of planarity and step coverage still remainunsolved.

Recently, in the high density mounting technologies including a chipsize package or a chip scale package (CSP) and a three-dimensionallamination, many studies have been done on a technique by which a finepattern having a high aspect ratio is formed on a substrate, followed bylaminating a metal such as copper to the obtained pattern to rewire froma chip. As the chip advances toward higher density and higherintegration, it is strongly desired in the rewiring technology to reducethe line width of a pattern and the size of a contact hole forconnecting between substrates. To obtain a fine pattern, a lithographytechnology is generally used, and in particular, a chemically amplifiednegative resist composition is suitable to obtain a fine pattern.Moreover, a pattern used for rewiring not only permanently existsbetween device chips but also needs to serve as a top coat that iscurable and also has excellent flexibility, heat resistance, electriccharacteristics, adhesiveness, reliability, and chemical resistance toprotect electric and electronic parts; and therefore, it is said thatthe resist composition to obtain the pattern is preferably of a negativetype.

As mentioned above, a chemically amplified negative resist compositionis suitable as the composition for a patterning process that is capableof processing a fine rewire and forming a top coat having excellentflexibility, heat resistance, electric characteristics, adhesiveness,reliability, and chemical resistance to protect electric and electronicparts.

On the other hand, the chemically amplified negative resist compositionthat is capable of forming a fine pattern to be used for processing arewire and is useful for a top coat to protect electric and electronicparts occasionally covers over a Cu wiring that has been previouslyprocessed on a substrate or over an Al electrode on a substrate. Inaddition, the substrates provided with a wire and an electrode includean insulating substrate such as SiN, which needs to be covered widely.However, adhesiveness between these substrates and a covering layerformed of the chemically amplified negative resist composition is notsufficient yet, so that there often occurs a problem that the coveringlayer formed of the resist composition is delaminated from thesubstrate.

Moreover, the chemically amplified negative resist composition usefulfor a top coat to protect electric and electronic parts requires analkaline aqueous solution or an organic solvent as a developer inpatterning, and the exposed part becomes insoluble in the developer by acrosslinking reaction or the like, while the unexposed part is easilysoluble in the developer. The negative resist composition used in recentyears exhibits small difference in solubility into the developer betweenthe exposed part and the unexposed part. In other words, the so-calleddissolution contrast therebetween is small. When the dissolutioncontrast is small, it cannot be expected to form a good patternsatisfying a further demand of a fine pattern in some cases. Inaddition, when the dissolution contrast is small, there is a fear that apattern cannot be formed on a substrate accurately according to a maskused in transferring and forming a pattern. Accordingly, the resistcomposition requires the highest dissolution contrast as possible, thatis, it is required to enhance the resolution.

Moreover, in the chemically amplified negative resist composition thatis capable of forming a fine pattern to be used for processing a rewireand is useful for the top coat to protect electric and electronic parts,sufficient solubility of the unexposed part in a developer such as analkaline aqueous solution or an organic solvent is important. In otherwords, if solubility of the unexposed part in a developer is poor, andin the case that the resist composition film to cover the substrate isthick, sometimes observed are the pattern deteriorations such as anundissolved residue or a scum in the pattern bottom, and a footingprofile in the pattern on the substrate. The scum and footing profilemay cause problems including disconnection of an electric circuit andwiring during a rewiring process; and thus, it is necessary to suppressthe generation of such problems.

Accordingly, drastic improvement of adhesiveness on a substrate isdesired while not only maintaining the fine patterning ability in therewiring technology required in accordance with the trends to higherdensity and higher integration of chips but also serving as a chemicallyamplified negative resist composition useful for a top coat to protectelectric and electronic parts. In addition, it is desired to quicklybuild up the system in which further improvement of resolution can beexpected and a scum and a footing profile are not generated in thepattern bottom.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-184571

Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-200315

SUMMARY OF THE INVENTION

The present invention was accomplished in view of the abovecircumstances, and an object thereof is to provide a siliconeskeleton-containing polymer compound suitably used as a base resin of achemically amplified negative resist composition that can remedy theproblem of delamination generated on a metal wiring such as Cu and Al,an electrode, and a substrate, especially on a substrate such as SiN,and can form a fine pattern without generating a scum and a footingprofile in the pattern bottom and on the substrate, and to furtherprovide a chemically amplified negative resist composition using thissilicone skeleton-containing polymer compound.

Another object of the present invention is to provide a patterningprocess in which the above-mentioned chemically amplified negativeresist composition is easily applied on a substrate by using a spincoating method to form a fine pattern.

Further object of the present invention is to provide a photo-curabledry film using the chemically amplified negative resist composition, amethod for producing the photo-curable dry film, a layered producthaving the photo-curable dry film laminated on a substrate, and apatterning process in which a resist layer having a wide range of filmthickness is formed by using the photo-curable dry film to form a finepattern even on a substrate having concavity and convexity.

Further object of the present invention is to provide a substrateprotected by a cured film that is obtained by post-curing a patternformed by the above-mentioned patterning process at low temperature.

Furthermore, the present invention has an object to provide asemiconductor apparatus having a cured film that is obtained bypost-curing a pattern formed by the above-mentioned patterning processat low temperature.

To accomplish the objects, the present invention provides a siliconeskeleton-containing polymer compound comprising a repeating unit shownby the general formula (1),

wherein R¹ to R⁴ may be the same or different, and represent amonovalent organic group having 1 to 15 carbon atoms and optionallycontaining an oxygen atom; R⁵ and R⁶ may be the same or different, andrepresent a monovalent organic group having 1 to 28 carbon atoms andoptionally containing an oxygen atom; “l” represents an integer of 0 to100; “m” represents an integer of 0 to 100; “n” represents an integer of1 or more; and T represents a divalent organic group shown by thegeneral formula (2),

wherein Q is any of

and the dotted line represents a bond.

Such a silicone skeleton-containing polymer compound can be suitablyused as a base resin of a chemically amplified negative resistcomposition that can remedy the problem of delamination generated on ametal wiring such as Cu and Al, an electrode, and a substrate,especially on a substrate such as SiN, and can form a fine patternwithout generating a scum and a footing profile in the pattern bottomand on the substrate.

It is preferred that the silicone skeleton-containing polymer compoundcontains a repeating unit shown by the general formula (3) and has aweight average molecular weight of 3,000 to 500,000,

wherein R¹ to R⁶, “l”, and “m” have the same meanings as above; “a”,“b”, “c”, “d”, “e”, “f”, “g”, and “h” are each 0 or a positive number,and “i” and “j” are each a positive number, provided thata+b+c+d+e+f+g+h+i+j=1; X is a divalent organic group shown by thegeneral formula (4); Y is a divalent organic group shown by the generalformula (5); W is a divalent organic group shown by the general formula(6); and U is a divalent organic group shown by the general formula (7);and T has the same meaning as above,

wherein Z represents a divalent organic group selected from any of

the dotted line represents a bond; “o” represents 0 or 1; R⁷ and R⁸ eachrepresent an alkyl group or an alkoxy group having 1 to 4 carbon atoms,and may be the same or different from each other; and “k” is 0, 1, or 2,

wherein V is a divalent organic group selected from any of

the dotted line represents a bond; “p” represents 0 or 1; R⁹ and R¹⁰each represent an alkyl group or alkoxy group having 1 to 4 carbonatoms, and may be the same or different from each other; and “q” is 0,1, or 2,

wherein the dotted line represents a bond; M represents an alkylenegroup having 1 to 12 carbon atoms or a divalent aromatic group; and R¹¹represents a hydrogen atom or a methyl group,

wherein the dotted line represents a bond; M and R¹¹ have the samemeanings as above; and R¹² represents a monovalent carboxyl-containingorganic group.

Such a silicone skeleton-containing polymer compound can be suitablyused as a base resin of a chemically amplified negative resistcomposition that can further remedy the problem of delaminationgenerated on a metal wiring such as Cu and Al, an electrode, and asubstrate, especially on a substrate such as SiN, and can form a finerpattern without generating a scum and a footing profile in the patternbottom and on the substrate.

R¹² in the general formula (7) is preferably a monovalentcarboxyl-containing organic group shown by the general formula (8),

wherein the dotted line represents a bond; R¹³ to R¹⁶ may be the same ordifferent, and represent a hydrogen atom, a halogen atom, a linear,branched, or cyclic alkyl group having 1 to 12 carbon atoms, or anaromatic group; R¹³ and R¹⁵ may be bonded respectively to R¹⁴ and R¹⁶ toform a substituted or unsubstituted ring structure having 1 to 12 carbonatoms; and “r” is any of 1 to 7.

The silicone skeleton-containing polymer compound like this can furtherenhance the effects of the present invention.

In the general formula (3), it is preferred that 0≤a≤0.5, 0≤b≤0.3,0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.8, 0≤h≤0.5, 0<i≤0.8, and0<j≤0.5.

Further, in the general formula (3), it is preferred that a=0, b=0, c=0,d=0, e=0, f=0, 0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and 0<j≤0.5.

A chemically amplified negative resist composition using such a siliconeskeleton-containing polymer compound is more excellent in adhesivenessto substrate, electric characteristics, and reliability.

Further, in the general formula (1) or the general formula (3), it ispreferred that “m” is an integer of 1 to 100; R¹ to R⁴ represent anidentical or different monovalent hydrocarbon group having 1 to 8 carbonatoms; R⁵ represents a phenyl substituent containing a hydroxyl group oran alkoxy group as shown by the general formula (9); R⁶ may be the sameor different from R¹ to R⁴, and represents a monovalent organic grouphaving 1 to 10 carbon atoms and optionally containing an oxygen atom, orR⁶ may be the same or different from R⁵, and represents a phenylsubstituent containing a hydroxyl group or an alkoxy group as shown bythe general formula (9),

wherein “s” is an integer of 0 to 10; and R¹⁷ represents a hydroxylgroup or a linear, branched, or cyclic alkoxy group having 1 to 12carbon atoms.

A chemically amplified negative resist composition using such a siliconeskeleton-containing polymer compound can improve the crosslinkingreactivity of the exposed part in patterning. Moreover, the improvementin crosslinking reactivity of the exposed part leads to low solubilityof the exposed part in the developer.

In this case, the phenyl substituent shown by the general formula (9) ispreferably one group, or two or more groups selected from the formula(10),

wherein the line with a wavy line represents a bonding arm.

A chemically amplified negative resist composition using such a siliconeskeleton-containing polymer compound can further improve thecrosslinking reactivity of the exposed part in patterning. Moreover, thefurther improvement in crosslinking reactivity of the exposed part leadsto lower solubility of the exposed part in the developer.

Further, it is preferred that the divalent organic group shown by thegeneral formula (6) is a divalent organic group shown by the generalformula (11), and the divalent organic group shown by the generalformula (7) is a divalent organic group shown by the general formula(12),

wherein the dotted line represents a bond; R¹¹ and R¹² have the samemeanings as above; and “t” represents a positive number of 1 to 12.

The compound containing such groups is suitable for thesilicone-skeleton containing polymer compound of the present invention.

Alternatively, it is preferred that the divalent organic group shown bythe general formula (6) is a divalent organic group shown by the generalformula (13), and the divalent organic group shown by the generalformula (7) is a divalent organic group shown by the general formula(14),

wherein the dotted line represents a bond; and R¹¹ and R¹² have the samemeanings as above.

The compound containing such groups is also suitable for thesilicone-skeleton containing polymer compound of the present invention.

In addition, the present invention provides a chemically amplifiednegative resist composition comprising:

(A) the above-mentioned silicone skeleton-containing polymer compound,

(B) a photosensitive acid generator capable of generating an acid bydecomposition with light having a wavelength of 190 to 500 nm;

(C) one or more crosslinking agents selected from an amino condensatemodified by formaldehyde or formaldehyde-alcohol, a phenol compoundhaving on average two or more methylol groups or alkoxymethylol groupsper molecule, a polyhydric phenol compound in which a hydrogen atom of aphenolic hydroxyl group is substituted by a glycidyl group, a polyhydricphenol compound in which a hydrogen atom of a phenolic hydroxyl group issubstituted by a substituent shown by the formula (C-1), and a compoundhaving two or more nitrogen atoms bonded to a glycidyl group as shown bythe formula (C-2),

wherein the dotted line represents a bond; R_(c) represents a linear,branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1or 2;

(D) a solvent; and

(E) a basic compound.

Such a chemically amplified negative resist composition can remedy theproblem of delamination generated on a metal wiring such as Cu and Al,an electrode, and a substrate, especially on a substrate such as SiN,and can form a fine pattern without generating a scum and a footingprofile in the pattern bottom and on the substrate.

In addition, the present invention provides a photo-curable dry filmcomprising a supporting film, a top coat film, and a photo-curable resinlayer having a film thickness of 10 to 100 μm, the photo-curable resinlayer being sandwiched between the supporting film and the top coatfilm, wherein the photo-curable resin layer is formed of theabove-mentioned chemically amplified negative resist composition.

Such a photo-curable dry film can form a fine pattern in wide ranges offilm thickness and wavelength, and a cured film obtained by post-curingat low temperature exhibits excellent flexibility, heat resistance,electric characteristics, adhesiveness, reliability, and chemicalresistance.

In addition, the present invention provides a method for producing aphoto-curable dry film, comprising:

(I) continuously applying the above-mentioned chemically amplifiednegative resist composition onto a supporting film to form aphoto-curable resin layer,

(II) continuously drying the photo-curable resin layer, and further

(III) laminating a top coat film onto the photo-curable resin layer.

The producing method like this is suitable to obtain the above-mentionedphoto-curable dry film.

In addition, the present invention provides a patterning processcomprising:

(1) applying the above-mentioned chemically amplified negative resistcomposition onto a substrate to form a photosensitive material film;

(2) exposing the photosensitive material film to a high energy beamhaving a wavelength of 190 to 500 nm or an electron beam via a photomaskafter a heat treatment; and

(3) subjecting to development by using an alkaline aqueous solution oran organic solvent as a developer after a heat treatment.

Such a patterning process can remedy the problem of delaminationgenerated on a metal wiring such as Cu and Al, an electrode, and asubstrate, especially on a substrate such as SiN, and can form a finepattern without generating a scum and a footing profile in the patternbottom and on the substrate. Also, application of the chemicallyamplified negative resist composition can be performed by a spin coatingmethod.

In addition, the present invention provides a patterning processcomprising:

(i) separating the top coat film from the above-mentioned photo-curabledry film and bringing an exposed photo-curable resin layer into closecontact with a substrate;

(ii) exposing the photo-curable resin layer to a high energy beam havinga wavelength of 190 to 500 nm or an electron beam via a photomask eitherthrough the supporting film or in a peeled-off state of the supportingfilm;

(iii) subjecting to a heat treatment after the exposure; and

(iv) subjecting to development by using an alkaline aqueous solution oran organic solvent as a developer.

Such a patterning process can remedy the problem of delaminationgenerated on a metal wiring such as Cu and Al, an electrode, and asubstrate, especially on a substrate such as SiN, and can form a finepattern without generating a scum and a footing profile in the patternbottom and on the substrate.

The patterning process preferably further comprises post-curing apatterned film formed by the development at 100 to 250° C. after thedevelopment.

The cured film thus obtained has excellent flexibility, adhesiveness tosubstrate, heat resistance, electric characteristics, mechanicalstrength, and chemical resistance to a soldering flux liquid, and thus,a semiconductor device having the cured film like this as the top coatexhibits a superior reliability, and especially, generation of cracksduring a thermal cycle test can be prevented.

At this time, the substrate may include a trench and/or a hole eachhaving an aperture width of 10 to 100 μm and a depth of 10 to 120 μm.

When the photo-curable dry film of the present invention is used, aresist film having a wide range of film thickness can be formed even ona substrate having concavity and convexity, so that a fine pattern canbe formed.

In addition, the present invention provides a layered product comprisinga substrate including a trench and/or a hole each having an aperturewidth of 10 to 100 μm and a depth of 10 to 120 μm, and the photo-curableresin layer of the above-mentioned photo-curable dry film laminated onthe substrate.

When such a layered product is employed, the pattern can be adequatelyembedded. Further, the layered product is excellent in variousproperties.

In addition, the present invention provides a substrate that isprotected by a film obtained by curing a pattern formed by theabove-mentioned patterning process.

Such a substrate is protected by the cured film having excellentflexibility, adhesiveness, heat resistance, electric characteristics,mechanical strength, chemical resistance, reliability, and crackresistance.

In addition, the present invention provides a semiconductor apparatuscomprising a film obtained by curing a pattern formed by theabove-mentioned patterning process.

Such a semiconductor apparatus has a cured film excellent inflexibility, adhesiveness, heat resistance, electric characteristics,mechanical strength, chemical resistance, reliability, and crackresistance.

As mentioned above, the present invention can provide a siliconeskeleton-containing polymer compound suitably used as a base resin of achemically amplified negative resist composition that can dramaticallyremedy the problem of delamination generated on a metal wiring such asCu and Al, an electrode, and a substrate, especially on a substrate suchas SiN, and a chemically amplified negative resist composition using thesilicone skeleton-containing polymer compound. Thus, the presentinvention can provide a chemically amplified negative resist compositionthat can form a fine pattern in a wide range of wavelength, enablesminiaturization of a pattern in the rewiring technology required inaccordance with the trends to higher density and higher integration ofchips, can prevent the generation of a scum and a footing profile in thepattern bottom on the substrate after patterning, and is useful for atop coat to protect electric and electronic parts; and further provide aphoto-curable dry film and a patterning process. In addition, when apattern obtained by the inventive patterning process is post-cured atlow temperature, there can be provided a substrate that is protected bya cured film having excellent flexibility, adhesiveness, heatresistance, electric characteristics, mechanical strength, chemicalresistance, reliability, and crack resistance, as well as asemiconductor apparatus having such a cured film.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an explanatory view of the adhesiveness measurement method inExamples.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As described above, there have been demanded a chemically amplifiednegative resist composition and a silicone skeleton-containing polymercompound suitably used as a base resin of the chemically amplifiednegative resist composition that can remedy the problem of delaminationgenerated on a metal wiring such as Cu and Al, an electrode, and asubstrate, especially on a substrate such as SiN, and can form a finepattern without generating a scum and a footing profile in the patternbottom and on the substrate.

The present inventors have earnestly investigated to achieve the aboveobjects, and consequently found that when a silicone skeleton-containingpolymer compound having a repeating unit shown by the general formula(1), in particular general formula (3), is used as a base resin of achemically amplified negative resist composition, a fine pattern can beformed and the problem of delamination generated on a metal wiring suchas Cu and Al, an electrode, and a substrate, especially on a substratesuch as SiN can be significantly remedied, thereby brought the presentinvention to completion.

Hereinafter, the present invention will be described in detail, but thepresent invention is not limited thereto.

(Silicone Skeleton-Containing Polymer Compound)

The silicone skeleton-containing polymer compound of the presentinvention has a repeating unit represented by the general formula (1),

wherein R¹ to R⁴ may be the same or different, and represent amonovalent organic group having 1 to 15 carbon atoms and optionallycontaining an oxygen atom; R⁵ and R⁶ may be the same or different, andrepresent a monovalent organic group having 1 to 28 carbon atoms andoptionally containing an oxygen atom; “l” represents an integer of 0 to100; “m” represents an integer of 0 to 100; “n” represents an integer of1 or more; and T represents a divalent organic group shown by thegeneral formula (2),

wherein Q is any of

and the dotted line represents a bond.

In the general formula (1), R¹ to R⁴ may be the same or different, andrepresent a monovalent organic group having 1 to 15 carbon atoms,preferably 1 to 10 carbon atoms, and optionally containing an oxygenatom. R⁵ and R⁶ may be the same or different, and represent a monovalentorganic group having 1 to 28 carbon atoms, preferably 1 to 15 carbonatoms, more preferably 1 to 10 carbon atoms, and optionally containingan oxygen atom. Illustrative examples thereof include linear, branchedor cyclic alkyl groups such as a methyl group, an ethyl group, a propylgroup, an isopropyl group, a n-butyl group, a tert-butyl group, and acyclohexyl group; linear, branched or cyclic alkenyl groups such as avinyl group, an allyl group, a propenyl group, a butenyl group, ahexenyl group, and a cyclohexenyl group; aryl groups such as a phenylgroup and a tolyl group; and aralkyl groups such as a benzyl group, aphenethyl group, and a methoxyphenethyl group. “l” represents an integerof 0 to 100, “m” represents an integer of 0 to 100, and “n” representsan integer of 1 or more.

It is preferred that the silicone skeleton-containing polymer compoundof the present invention contains a repeating unit shown by the generalformula (3) and has a weight average molecular weight of 3,000 to500,000,

wherein R¹ to R⁶, “l”, and “m” have the same meanings as above; “a”,“b”, “c”, “d”, “e”, “f”, “g”, and “h” are each 0 or a positive number,and “i” and “j” are each a positive number, provided thata+b+c+d+e+f+g+h+i+j=1; X is a divalent organic group shown by thegeneral formula (4); Y is a divalent organic group shown by the generalformula (5); W is a divalent organic group shown by the general formula(6); and U is a divalent organic group shown by the general formula (7);and T has the same meaning as above,

wherein Z represents a divalent organic group selected from any of

the dotted line represents a bond; “o” represents 0 or 1; R⁷ and R⁸ eachrepresent an alkyl group or an alkoxy group having 1 to 4 carbon atoms,and may be the same or different from each other; and “k” is 0, 1, or 2,

wherein V is a divalent organic group selected from any of

the dotted line represents a bond; “p” represents 0 or 1; R⁹ and R¹⁰each represent an alkyl group or alkoxy group having 1 to 4 carbonatoms, and may be the same or different from each other; and “q” is 0,1, or 2,

wherein the dotted line represents a bond; M represents an alkylenegroup having 1 to 12 carbon atoms or a divalent aromatic group; and R¹¹represents a hydrogen atom or a methyl group,

wherein the dotted line represents a bond; M and R¹¹ have the samemeanings as above; and R¹² represents a monovalent carboxyl-containingorganic group.

In view of the compatibility with a later-described crosslinking agentand photosensitive acid generator, and in view of photo-curability, “l”is an integer of 0 to 100, preferably 1 to 80, and “m” is an integer of0 to 100, preferably 1 to 100, more preferably 1 to 80. “a”, “b”, “c”,“d”, “e”, “f”, “g”, and “h” are each 0 or a positive number, “i” and “j”are each a positive number, and a+b+c+d+e+f+g+h+i+j=1. In view ofadhesiveness to substrate, electric characteristics, and reliability, itis preferred that 0≤a≤0.5, 0≤b≤0.3, 0≤c<0.5, 0≤d<0.3, 0≤e≤0.8, 0≤f≤0.5,0≤g≤0.8, 0≤h≤0.5, 0<i≤0.8, and 0<j≤0.5, particularly preferably a=0,b=0, c=0, d=0, e=0, f=0, 0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and 0<j≤0.5.

R¹² in the general formula (7) is preferably a monovalentcarboxyl-containing organic group shown by the general formula (8),

wherein the dotted line represents a bond; R¹³ to R¹⁶ may be the same ordifferent, and represent a hydrogen atom, a halogen atom, a linear,branched, or cyclic alkyl group having 1 to 12 carbon atoms, or anaromatic group; R¹³ and R¹⁵ may be bonded respectively to R¹⁴ and R¹⁶ toform a substituted or unsubstituted ring structure having 1 to 12 carbonatoms; and “r” is any of 1 to 7.

Further, in the general formula (1) or the general formula (3), it ispreferred that “m” is an integer of 1 to 100, preferably 1 to 80; R¹ toR⁴ represent an identical or different monovalent hydrocarbon grouphaving 1 to 8 carbon atoms; R⁵ represents a phenyl substituentcontaining a hydroxyl group or an alkoxy group as shown by the generalformula (9); R⁶ may be the same or different from R¹ to R⁴, andrepresents a monovalent organic group having 1 to 10 carbon atoms,preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms,and optionally containing an oxygen atom, or R⁶ may be the same ordifferent from R⁵, and represents a phenyl substituent containing ahydroxyl group or an alkoxy group as shown by the general formula (9),

wherein “s” is an integer of 0 to 10; and R¹⁷ represents a hydroxylgroup or a linear, branched, or cyclic alkoxy group having 1 to 12carbon atoms.

In the phenyl substituent shown by the general formula (9), the hydroxylgroup or the alkoxy group may be substituted in any of o-, m-, andp-positions. If R¹⁷ represents an alkoxy group, the number of carbonatoms is 1 to 12, preferably 1 to 4.

The phenyl substituent shown by the general formula (9) may bespecifically exemplified by groups shown by the formula (10). In theformula (10), the line with a wavy line:

represents a bonding arm.

In addition, it is preferred that the divalent organic group shown bythe general formula (6) is a divalent organic group shown by the generalformula (11), and the divalent organic group shown by the generalformula (7) is a divalent organic group shown by the general formula(12),

wherein the dotted line represents a bond; R¹¹ and R¹² have the samemeanings as above; and “t” represents a positive number of 1 to 12.

Alternatively, it is preferred that the divalent organic group shown bythe general formula (6) is a divalent organic group shown by the generalformula (13), and the divalent organic group shown by the generalformula (7) is a divalent organic group shown by the general formula(14),

wherein the dotted line represents a bond; and R¹¹ and R¹² have the samemeanings as above.

The silicone skeleton-containing polymer compound of the presentinvention should have a weight average molecular weight of 3,000 to500,000, preferably 5,000 to 300,000, in view of the compatibility andthe photo-curability of a later-described chemically amplified negativeresist composition using it, and in view of mechanical characteristicsof a cured product obtained from the chemically amplified negativeresist composition. Herein, the weight average molecular weight isdetermined by gel permeation chromatography (GPC) in terms ofpolystyrene.

The silicone skeleton-containing polymer compound of the presentinvention can be produced, for example, by polymerization reaction ofthe following compounds in the presence of a catalyst to synthesize asilicone skeleton-containing polymer compound having an alcoholic orphenolic hydroxyl group, and if necessary, followed by reacting a partor all of the alcoholic or phenolic hydroxyl groups of the synthesizedsilicone skeleton-containing polymer compound with a dicarboxylic acidanhydride to introduce a carboxyl group:

a hydrogensilphenylene (1,4-bis(dimethylsilyl)benzene) shown by theformula (15)

a dihydroorganosiloxane shown by the general formula (16)

wherein R³, R⁴, R⁵, R⁶, “l” and “m” have the same meanings as definedabove;

an optional specific phenol compound having two allyl groups and shownby the general formula (17)

wherein Z, R⁷, R⁸, “o” and “k” have the same meanings as defined above;

an optional specific epoxy-containing compound having two allyl groupsand shown by the general formula (18)

wherein V, R⁹, R¹⁰, “p” and “q” have the same meanings as defined above;

an optional specific phenol compound having two allyl groups and shownby the general formula (19)

wherein M and R¹¹ have the same meanings as defined above; and

an optional specific phenol compound having two allyl groups and shownby the general formula (20)

wherein Q has the same meaning as defined above.

The compound shown by the general formula (16) can be obtained byhydrolysis condensation of a silane compound shown by the formula (21),followed by hydrolysis with an organosiloxane having an intendedskeletal structure.

The hydrolysis condensation may be performed by the generally knownhydrolysis condensation method of a silane compound.

wherein R⁶, R¹⁷, and “s” have the same meanings as defined above; andR¹⁸ represents a halogen atom or an alkoxy group having 1 to 4 carbonatoms.

As the phenol compound having two allyl groups and shown by the generalformula (19), a compound shown by the general formula (22) or a compoundshown by the general formula (23) is preferable,

wherein R¹¹ and “t” have the same meanings as defined above,

wherein R¹¹ has the same meaning as defined above.

The weight average molecular weight of the silicone skeleton-containingpolymer compound of the present invention can be easily controlled byadjusting a ratio of the total number of allyl groups in the specificphenol compound having two allyl groups of the formula (17), thespecific epoxy-containing compound having two allyl groups of theformula (18), the specific phenol compound having two allyl groups ofthe formula (19), and the specific phenol compound having two allylgroups of the formula (20) to the total number of hydrosilyl groups inthe hydrogensilphenylene of formula (15) and the dihydroorganosiloxaneof formula (16) (i.e., total allyl groups/total hydrosilyl groups).Alternatively, the weight average molecular weight can be easilycontrolled by polymerization of a specific phenol compound having twoallyl groups, a specific epoxy-containing compound having two allylgroups, hydrogensilphenylene, and dihydroorganosiloxane while using amonoallyl compound (e.g., o-allylphenol), a monohydrosilane (e.g.,triethylhydrosilane) or monohydrosiloxane as a molecular weightmodifier.

Examples of the catalyst which can be used in the polymerizationreaction include platinum group metal elements such as platinum(including platinum black), rhodium, and palladium; platinum chloride,chloroplatinic acid, and chloroplatinic acid salts such as H₂PtCl₄.xH₂O,H₂PtCl₆.xH₂O, NaHPtCl₆.xH₂O, KHPtCl₆.xH₂O, Na₂PtCl₆.xH₂O, K₂PtCl₄.xH₂O,PtCl₄.xH₂O, PtCl₂, Na₂HPtCl₄.xH₂O (wherein x is preferably an integer of0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinicacid (U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid witholefins (U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662, and U.S. Pat.No. 3,775,452); platinum group metals such as platinum black andpalladium on supports such as alumina, silica and carbon; rhodium-olefincomplexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson'scatalyst); and complexes of platinum chloride, chloroplatinic acid, orchloroplatinic acid salts with vinyl-containing siloxanes (particularly,vinyl-containing cyclic siloxanes).

The amount thereof to be used is a catalytic amount, and in general, itis preferably in the range of 0.001 to 0.1% by mass in terms of aplatinum group metal based on the total amount of the reaction polymer.

In the polymerization reaction, a solvent may be used, if necessary.Preferable examples of the solvent include hydrocarbon solvents such astoluene and xylene.

With respect to polymerization conditions, the polymerizationtemperature is preferably in the range of 40 to 150° C., more preferably60 to 120° C. since the catalyst is not deactivated and thepolymerization can be brought to completion in a short time.

Although the polymerization time depends on the type and amount of adesired polymer, polymerization is preferably completed within about 0.5to 100 hours, more preferably about 0.5 to 30 hours, in order to preventmoisture entry into the polymerization system. After completion of thepolymerization, the solvent is distilled off if the solvent is used. Inthis way, a silicone skeleton-containing polymer compound having arepeating unit shown by the general formula (3) can be obtained.

When the weight average molecular weight of the siliconeskeleton-containing polymer compound is lowered, the viscosity of thesilicone skeleton-containing polymer compound is also lowered.Therefore, the viscosity of the resin layer formed from the chemicallyamplified negative resist composition using the siliconeskeleton-containing polymer compound is also lowered. Moreover, in themolecule of the silicone skeleton-containing polymer compound, when theproportion of the molecular units containing linear polysiloxane (i.e.“b”, “d”, “f”, “h”, and “j” in the general formula (3)) is increased,the proportion of the molecular units containing aromatic compound suchas silphenylene (i.e. “a”, “c”, “e”, “g”, and “i” in the general formula(3)) is relatively decreased, which results in low viscosity of thesilicone skeleton-containing polymer compound. Therefore, the viscosityof the resin layer formed from the chemically amplified negative resistcomposition using the silicone skeleton-containing polymer compound isalso lowered. Furthermore, in the molecule of the siliconeskeleton-containing polymer compound, when the chain length of thelinear polysiloxane is increased, i.e., when the value of “l” and “m” inthe general formula (3) is increased, the viscosity of the siliconeskeleton-containing polymer compound is lowered. Therefore, theviscosity of the resin layer formed from the chemically amplifiednegative resist composition using the silicone skeleton-containingpolymer compound is also lowered.

Next, explanation is given about the reaction for introducing a carboxylgroup by reacting a part or all of hydroxyl groups of the siliconeskeleton-containing polymer compound having an alcoholic or phenolichydroxyl group that is synthesized by the hydrosilylation polymerizationreaction, with a dicarboxylic acid anhydride.

For the reaction of a part or all of hydroxyl groups of the siliconeskeleton-containing polymer compound having an alcoholic or phenolichydroxyl group obtained by the hydrosilylation polymerization reactionwith a dicarboxylic acid anhydride, first, the obtained siliconeskeleton-containing polymer compound is dissolved in a solvent having aweight 3 times of the compound. Then, an appropriate molar equivalent ofdicarboxylic acid anhydride is added to molar ratios e and f of W in thegeneral formula (3) (i.e., a unit having an alcoholic or phenolichydroxyl group), and 1 equivalent triethylamine is added to the unithaving an alcoholic or phenolic hydroxyl group. The resulting mixture isstirred at a temperature ranging from room temperature to 50° C. forseveral hours to perform the reaction, whereby a carboxyl group can beintroduced into the silicone skeleton-containing polymer compound. Forexample, if the dicarboxylic acid anhydride to be reacted is1-equivalent, a carboxyl group is introduced to all alcoholic orphenolic hydroxyl groups of W unit in the general formula (3), whichleads to the general formula (3) wherein e=0 and f=0. The introducingratio of carboxyl group, i.e., the preferable ranges of “g” and “h” inthe general formula (3) are as described above.

The carboxylic acid thus introduced is shown by U in the general formula(3), and U is shown by the general formula (7). Further, R¹² in thegeneral formula (7) can be shown by the general formula (8),

wherein the dotted line represents a bond; R¹³ to R¹⁶ may be the same ordifferent, and represent a hydrogen atom, a halogen atom, a linear,branched, or cyclic alkyl group having 1 to 12 carbon atoms, or anaromatic group; R¹³ and R¹⁵ may be bonded respectively to R¹⁴ and R¹⁶ toform a substituted or unsubstituted ring structure having 1 to 12 carbonatoms; and “r” is any of 1 to 7.

The dicarboxylic acid anhydride to be reacted with a part or all ofhydroxyl groups of the silicone skeleton-containing polymer compoundhaving an alcoholic or phenolic hydroxyl group can be shown by thegeneral formula (24),

wherein R¹³ to R¹⁶ and “r” have the same meanings as defined above.

Preferable examples of the dicarboxylic acid anhydride include succinicanhydride, phthalic anhydride, maleic anhydride, itaconic anhydride,glutaric anhydride, adipic anhydride, pimelic anhydride, subericanhydride, azelaic anhydride, sebacic anhydride, and compounds havingthe following structures.

For example, the silicone skeleton-containing polymer compound obtainedby the above method has a phenol phthalein skeleton or a phenol redskeleton shown by the general formula (2). Such a siliconeskeleton-containing polymer compound of the present invention issuitable as a base resin of a chemically amplified negative resistcomposition, and can remedy the problem of delamination generated on ametal wiring such as Cu and Al, an electrode, and a substrate,especially on a substrate such as SiN. It is supposed that thedelamination can be remedied because a carbonyl group or a sulfonylgroup in the general formula (2) introduced into the siliconeskeleton-containing polymer compound enhances the interaction with thesubstrate.

In addition, the introduction of the structural part shown by thegeneral formula (2) into the silicone skeleton-containing polymercompound provides a high Tg, excellent mechanical strength, andreliability to the cured film due to the rigid structure thereof, andalso enhances the solubility into a developer of an alkaline aqueoussolution such as an aqueous tetramethyl ammonium hydroxide (TMAH)solution, which is generally used for a chemically amplified negativeresist composition. It is supposed that the solubility is enhancedbecause when the system becomes alkaline, the general formula (2) isring-opened, thereby generating a carboxylic acid or a sulfonic acid. Incontrast, when a rigid structure other than the structural part shown bythe general formula (2) is used to obtain a cured film with a high Tg,excellent mechanical strength, and reliability, the solubility into anaqueous alkaline solution is remarkably deteriorated.

The chemically amplified negative resist composition requires a highsolubility of the unexposed part in a developer. That is, in thedevelopment of a fine pattern, if the solubility of the unexposed partin a developer is low, an undissolved residue in the pattern bottom anda footing profile between the pattern and the substrate may occur.However, when a pattern is formed by using the chemically amplifiednegative resist composition containing the silicone skeleton-containingpolymer compound of the present invention, the solubility of theunexposed part in an aqueous alkaline developer is improved, andtherefore, the problems such as the occurrence of an undissolved residuein the pattern bottom and a footing profile can be resolved, asmentioned above.

On the other hand, when the inventive silicone skeleton-containingpolymer compound having the phenyl substituent shown by the generalformula (9) is used as the base resin of a chemically amplified negativeresist composition, crosslinking reactivity of the exposed part can beimproved in the pattern formation. This is considered because thecrosslinking point in the silicone skeleton-containing polymer compoundis remarkably increased due to the additional crosslinking point on thesiloxane, and thus the reaction with a later-described crosslinkingagent progresses more greatly. In this way, the improvement incrosslinking reactivity of the exposed part causes a low solubility ofthe exposed part in a developer.

As mentioned above, by using the silicone skeleton-containing polymercompound of the present invention as the base resin of a chemicallyamplified negative resist composition, solubility of the unexposed partin a developer can be improved, and further, the solubility of theexposed part in a developer can be extremely reduced. Thus, thedifference in dissolution rate between the exposed part and theunexposed part can be increased, and the dissolution contrast can beenhanced. Accordingly, a finer pattern formation is expected. That is,the silicone skeleton-containing polymer compound of the presentinvention is suitable as the base resin of a chemically amplifiednegative resist composition.

(Chemically Amplified Negative Resist Composition)

Further, the present invention provides a chemically amplified negativeresist composition comprising:

(A) the above-mentioned silicone skeleton-containing polymer compound,

(B) a photosensitive acid generator capable of generating an acid bydecomposition with light having a wavelength of 190 to 500 nm;

(C) one or more crosslinking agents selected from an amino condensatemodified by formaldehyde or formaldehyde-alcohol, a phenol compoundhaving on average two or more methylol groups or alkoxymethylol groupsper molecule, a polyhydric phenol compound in which a hydrogen atom of aphenolic hydroxyl group is substituted by a glycidyl group, a polyhydricphenol compound in which a hydrogen atom of a phenolic hydroxyl group issubstituted by a substituent shown by the formula (C-1), and a compoundhaving two or more nitrogen atoms bonded to a glycidyl group as shown bythe formula (C-2),

wherein the dotted line represents a bond; R_(c) represents a linear,branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1or 2;

(D) a solvent; and

(E) a basic compound.

As to (B) the photosensitive acid generator, a compound capable ofgenerating an acid by exposure to light having a wavelength of 190 to500 nm thereby serving as a curing catalyst may be used. The siliconeskeleton-containing polymer compound of the present invention hasexcellent compatibility with a photosensitive acid generator, so thatvarious photosensitive acid generators can be used.

Illustrative examples of the photosensitive acid generator include anonium salt, a diazomethane derivative, a glyoxime derivative, a3-ketosulfone derivative, a disulfone derivative, a nitrobenzylsulfonatederivative, a sulfonate ester derivative, an imide-yl-sulfonatederivative, an oximesulfonate derivative, an iminosulfonate derivative,and a triazine derivative.

The onium salt may be exemplified by a compound shown by the generalformula (25),(R¹⁹)_(u)G⁺K⁻  (25)wherein R¹⁹ represents an optionally substituted linear, branched, orcyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; G⁺represents an iodonium or a sulfonium; and K⁻ represents anon-nucleophilic counter ion; and “u” is 2 or 3.

In R¹⁹, illustrative examples of the alkyl group include a methyl group,an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a2-oxocyclohexyl group, a norbornyl group, and an adamantyl group.Illustrative examples of the aryl group include a phenyl group; alkoxyphenyl groups such as an o-, m-, or p-methoxyphenyl group, an o-, m-, orp-ethoxyphenyl group, and a m- or p-tert-butoxyphenyl group; and alkylphenyl groups such as a 2-, 3-, or 4-methylphenyl group, a 2-, 3-, or4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group,and a dimethylphenyl group. Illustrative examples of the aralkyl groupinclude a benzyl group and a phenethyl group.

Illustrative examples of the non-nucleophilic counter ion K⁻ includehalide ions such as a chloride ion and a bromide ion; fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, andnonafluorobutane sulfonate; aryl sulfonates such as tosylate,benzenesulfonate, 4-fluorobenzenesulfonate, and1,2,3,4,5-pentafluorobenzenesulfonate; and alkyl sulfonates such asmesylate and butanesulfonate.

The diazomethane derivative may be exemplified by a compound shown bythe general formula (26),

wherein each R²⁰ may be the same or different, and represents a linear,branched, or cyclic alkyl group or halogenated alkyl group having 1 to12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

In R²⁰, illustrative examples of the alkyl group include a methyl group,an ethyl group, a propyl group, a butyl group, an amyl group, acyclopentyl group, a cyclohexyl group, a norbornyl group, and anadamantyl group. Illustrative examples of the halogenated alkyl groupinclude a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a1,1,1-trichloroethyl group, and a nonafluorobutyl group. Illustrativeexamples of the aryl group include a phenyl group; alkoxyphenyl groupssuch as an o-, m-, or p-methoxyphenyl group, an o-, m-, orp-ethoxyphenyl group, and a m- or p-tert-butoxyphenyl group; andalkylphenyl groups such as a 2-, 3-, or 4-methylphenyl group, a 2-, 3-,or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenylgroup, and a dimethylphenyl group. Illustrative examples of thehalogenated aryl group include a fluorophenyl group, a chlorophenylgroup, and a 1,2,3,4,5-pentafluorophenyl group. Illustrative examples ofthe aralkyl group include a benzyl group and a phenethyl group.

Illustrative examples of the photosensitive acid generator include oniumsalts such as diphenyliodonium trifluoromethanesulfonate,(p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate,diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodoniump-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate,(p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate,bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate,tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate,triphenylsulfonium p-toluenesulfonate,(p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate,bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate,tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate,triphenylsulfonium nonafluolobutanesulfonate, triphenylsulfoniumbutanesulfonate, trimethylsulfonium trifluoromethanesulfonate,trimethylsulfonium p-toluenesulfonate,cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate,cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate,dimethylphenylsulfonium trifluoromethanesulfonate,dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfoniumtrifluoromethanesulfonate, dicyclohexylphenylsulfoniump-toluenesulfonate, and diphenyl(4-thiophenoxyphenyl)sulfoniumhexafluoroantimonate; diazomethane derivatives such asbis(benzenesulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane,bis(xylenesulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane,bis(cyclopentylsulfonyl) diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl) diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl) diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl) diazomethane, bis(n-amylsulfonyl)diazomethane, bis(isoamylsulfonyl) diazomethane, bis(sec-amylsulfonyl)diazomethane, bis(tert-amylsulfonyl) diazomethane,1-cyclohexylsulfonyl-1-(tert-butylsulfonyl) diazomethane,1-cyclohexylsulfonyl-1-(tert-amylsulfonyl) diazomethane, and1-tert-amylsulfonyl-1-(tert-butylsulfonyl) diazomethane; glyoximederivatives such as bis-o-(p-toluenesulfonyl)-α-dimethyl glyoxime,bis-o-(p-toluenesulfonyl)-α-diphenyl glyoxime,bis-o-(p-toluenesulfonyl)-α-dicyclohexyl glyoxime,bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime,bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime,bis-o-(n-butanesulfonyl)-α-dimethyl glyoxime,bis-o-(n-butanesulfonyl)-α-diphenyl glyoxime,bis-o-(n-butanesulfonyl)-α-dicyclohexyl glyoxime,bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime,bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime,bis-o-(methanesulfonyl)-α-dimethyl glyoxime,bis-o-(trifluoromethanesulfonyl)-α-dimethyl glyoxime,bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethyl glyoxime,bis-o-(tert-butanesulfonyl)-α-dimethyl glyoxime,bis-o-(perfluorooctanesulfonyl)-α-dimethyl glyoxime,bis-o-(cyclohexanesulfonyl)-α-dimethyl glyoxime,bis-o-(benzenesulfonyl)-α-dimethyl glyoxime,bis-o-(p-fluorobenzenesulfonyl)-α-dimethyl glyoxime,bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethyl glyoxime,bis-o-(xylenesulfonyl)-α-dimethyl glyoxime, andbis-o-(camphersulfonyl)-α-dimethyl glyoxime; oxime sulfonate derivativessuch as α-(benzenesulfoniumoxyimino)-4-methylphenylacetonitrile; β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl) propane; disulfonederivatives such as diphenyl disulfone and dicyclohexyl disulfone;nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzylp-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonateester derivatives such as 1,2,3-tris(methanesulfonyloxy)benzene,1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and1,2,3-tris(p-toluenesulfonyloxy)benzene; imide-yl-sulfonate derivativessuch as phthalimide-yl-triflate, phthalimide-yl-tosylate, 5-norbornene2,3-dicarboxyimide-yl-triflate, 5-norbornene2,3-dicarboxyimide-yl-tosylate, 5-norbornene2,3-dicarboxyimide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide; iminosulfonates such as(5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrileand(5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile;and 2-methyl-2[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane. Amongthem, imide-yl-sulfonates, iminosulfonates, and oximesulfonates arepreferably used.

Meanwhile, these photosensitive acid generators can be used solely or asa mixture of two or more kinds.

In view of the light absorption of the photosensitive acid generatoritself and the photo-curability in a thick film, the formulation amountof the photosensitive acid generator is preferably in the range of 0.05to 20 parts by mass, particularly preferably 0.2 to 5 parts by mass,based on 100 parts by mass of (A) the silicone-skeleton containingpolymer compound.

As to (C) the crosslinking agent, one or more crosslinking agentsselected from an amino condensate modified by formaldehyde orformaldehyde-alcohol, a phenol compound having on average two or moremethylol groups or alkoxymethylol groups per molecule, a polyhydricphenol compound in which a hydrogen atom of a phenolic hydroxyl group issubstituted by a glycidyl group, a polyhydric phenol compound in which ahydrogen atom of a phenolic hydroxyl group is substituted by asubstituent shown by the formula (C-1) and preferably containing two ormore of the substituents, and a compound having two or more nitrogenatoms bonded to a glycidyl group and shown by the formula (C-2), may beused,

wherein the dotted line represents a bond; R_(c) represents a linear,branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1or 2.

The amino condensate modified by formaldehyde or formaldehyde-alcoholmay be exemplified by melamine condensates modified by formaldehyde orformaldehyde-alcohol and urea condensates modified by formaldehyde orformaldehyde-alcohol.

To synthesize a melamine condensate modified by formaldehyde orformaldehyde-alcohol, for example, a melamine monomer is modified byformalin into a methylol form, and optionally, the resultant compound isfurther modified by an alcohol into an alkoxy form according to a knownmethod, thereby obtaining a modified melamine shown by the formula (27).In this case, lower alcohols such as an alcohol having 1 to 4 carbonatoms are preferred as the alcohol.

In the above formula, each R²¹ may be the same or different, andrepresents a methylol group, an alkoxymethyl group containing an alkoxygroup having 1 to 4 carbon atoms, or a hydrogen atom, provided that oneor more of them is a methylol group or an alkoxymethyl group.

Examples of R²¹ include a methylol group, alkoxymethyl groups such as amethoxymethyl group and an ethoxymethyl group, and a hydrogen atom.

Illustrative examples of the modified melamine shown by the formula (27)include trimethoxymethyl monomethylol melamine, dimethoxymethylmonomethylol melamine, trimethylol melamine, hexamethylol melamine, andhexamethoxymethylol melamine.

Then, the modified melamine shown by the formula (27) or the multimericcompound thereof (e.g. oligomer including dimer and trimer) ispolymerized by addition condensation with formaldehyde until a desiredmolecular weight is achieved according to a known method, therebyobtaining the melamine condensate modified by formaldehyde orformaldehyde-alcohol.

Also, an urea condensate modified by formaldehyde orformaldehyde-alcohol can be synthesized by modifying an urea condensatehaving a desired molecular weight with formaldehyde into a methylolform, and optionally, further modifying the resultant compound with analcohol into an alkoxy form, according to a known method.

Illustrative examples of the urea condensate modified by formaldehyde orformaldehyde-alcohol include a methoxymethylated urea condensate, anethoxymethylated urea condensate, and a propoxymethylated ureacondensate.

These modified melamine condensates and modified urea condensates may beused solely or as a mixture of two or more kinds.

The phenol compound having on average two or more methylol groups oralkoxymethylol groups per molecule may be exemplified by(2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2′,6,6′-tetramethoxymethylbisphenol A, compounds shown by the formulae (C-3) to (C-7), and thelike.

The polyhydric phenol compound in which a hydrogen atom of a phenolichydroxyl group is substituted by a glycidyl group may be exemplified bycompounds that are obtained by reacting a hydroxyl group of bisphenol A,tris(4-hydroxyphenyl)methane, or 1,1,1-tris(4-hydroxyphenyl)ethane withepichlorohydrin in the presence of a base. Preferable examples of thepolyhydric phenol compound in which a hydrogen atom of a phenolichydroxyl group is substituted by a glycidyl group include compoundsshown by the formulae (C-8) to (C-14),

wherein 2≤v≤3.

These polyhydric phenol compounds in which a hydrogen atom of a phenolichydroxyl group is substituted by a glycidyl group may be used as acrosslinking agent solely or as a mixture of two kinds.

Also, the polyhydric phenol compound in which a hydrogen atom of aphenolic hydroxyl group is substituted by a substituent shown by theformula (C-1) and containing two or more of the substituents may beexemplified by a compound shown by the formula (C-15),

wherein the dotted line represents a bond,

wherein 1≤w≤3.

On the other hand, the compound having two or more nitrogen atoms bondedto a glycidyl group and shown by the formula (C-2) may be exemplified bya compound shown by the formula (C-16),

wherein the dotted line represents a bond; R_(c) represents a linear,branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1or 2,

wherein J represents a linear, branched, or cyclic alkylene group having2 to 12 carbon atoms, or a divalent aromatic group.

Illustrative examples of the compound shown by the formula (C-16)include compounds shown by the formulae (C-17) to (C-20).

Other examples of the compound having two or more nitrogen atoms bondedto a glycidyl group and shown by the formula (C-2) include a compoundshown by the formula (C-21).

These compounds having two or more nitrogen atoms bonded to a glycidylgroup and shown by the formula (C-2) may be used as a crosslinking agentsolely or as a mixture of two kinds.

The above-mentioned crosslinking agent serves to initiate the curingreaction with (A) the silicone skeleton-containing polymer compound,facilitates the pattern formation, and enhances strength of the curedproduct. The weight average molecular weight of the crosslinking agentis preferably in the range of 150 to 10,000, particularly preferably 200to 3,000, in view of photo-curability and heat resistance.

The crosslinking agent may be used solely or a mixture of two or morekinds.

Also, in view of photo-curability and reliability as the top coat toprotect electric and electronic parts after post-cure, the amount of thecrosslinking agent to be blended is preferably in the range of 0.5 to 50parts by mass, more preferably 1 to 30 parts by mass based on 100 partsby mass of (A) the silicone skeleton-containing polymer compound.

As to (D) the solvent, those capable of dissolving (A) the siliconeskeleton-containing polymer compound, (B) the photosensitive acidgenerator, and (C) the crosslinking agent can be used.

Illustrative examples of the solvent include ketones such ascyclohexanone, cyclopentanone, and methyl-2-n-amylketone; alcohols suchas 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol,and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethylether, ethylene glycol monomethyl ether, propylene glycol monoethylether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether,and diethylene glycol dimethyl ether; and esters such as propyleneglycol monomethyl ether acetate, propylene glycol monoethyl etheracetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate,and γ-butyrolactone; and these may be used one or more kinds. Amongthem, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycolmonomethyl ether acetate, and γ-butyrolactone, or a mixture of them areparticularly preferred, because these materials have the utmostsolubility to the photosensitive acid generator.

In view of compatibility, viscosity, and coating properties of thechemically amplified negative resist composition, the amount of thesolvent to be blended is preferably in the range of 50 to 2,000 parts bymass, more preferably 100 to 1,000 parts by mass based on 100 parts bymass of the total amount of (A) the silicone skeleton-containing polymercompound, (B) the photosensitive acid generator, and (C) thecrosslinking agent.

Moreover, in the chemically amplified negative resist composition of thepresent invention, (E) a basic compound may be added if necessary. Asthe basic compound, a compound capable of suppressing diffusion rate ofan acid that is generated from the photosensitive acid generator in theresist film is suitable. By blending the basic compound like this, theresolution can be enhanced, the sensitivity change after exposure can besuppressed, and dependence on a substrate and an environment can be madesmall, so that the exposure allowance, the pattern shape, and the likemay be improved.

Illustrative examples of the basic compound include primary, secondary,and tertiary aliphatic amines, mixed amines, aromatic amines,heterocyclic amines, a nitrogen-containing compound having a carboxylgroup, a nitrogen-containing compound having a sulfonyl group, anitrogen-containing compound having a hydroxyl group, anitrogen-containing compound having a hydroxyphenyl group, anitrogen-containing alcoholic compound, an amide derivative, an imidederivative, and a compound shown by the general formula (28).N(α)_(y)(β)_(3-y)  (28)

In the above formula, “y” is 1, 2, or 3. The side chain α may be thesame or different and represents a substituent shown by any of thegeneral formulae (29) to (31). The side chain β may be the same ordifferent and represents a hydrogen atom, or a linear, branched, orcyclic alkyl group having 1 to 20 carbon atoms and optionally containingan ether bond or a hydroxyl group. Further, the side chains a may bebonded with each other to form a ring,

wherein R³⁰⁰, R³⁰², and R³⁰⁵ represent a linear or branched alkylenegroup having 1 to 4 carbon atoms; and R³⁰¹ and R³⁰⁴ represent a hydrogenatom or a linear, branched, or cyclic alkyl group having 1 to 20 carbonatoms and optionally containing one or more of a hydroxyl group, anether bond, an ester bond, and a lactone ring. R³⁰³ represents a singlebond, or a linear or branched alkylene group having 1 to 4 carbon atoms;and R³⁰⁶ represents a linear, branched, or cyclic alkyl group having 1to 20 carbon atoms and optionally containing one or more of a hydroxylgroup, an ether bond, an ester bond, and a lactone ring. Meanwhile, thesymbol * shows the bond terminal.

Illustrative examples of the primary aliphatic amines include ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, pentylamine,tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine,heptylamine, octylamine, nonylamine, decylamine, dodecylamine,cetylamine, methylenediamine, ethylenediamine, andtetraethylenepentamine.

Illustrative examples of the secondary aliphatic amines includedimethylamine, diethylamine, di-n-propylamine, diisopropylamine,di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine,dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine,dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine,N,N-dimethylmethylene diamine, N,N-dimethylethylene diamine, andN,N-dimethyltetraethylene pentamine.

Illustrative examples of the tertiary aliphatic amines includetrimethylamine, triethylamine, tri-n-propylamine, triisopropylamine,tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine,tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine,trioctylamine, trinonylamine, tridecylamine, tridodecylamine,tricetylamine, N,N,N′,N′-tetramethylmethylene diamine,N,N,N′,N′-tetramethylethylene diamine, andN,N,N′,N′-tetramethyltetraethylene pentamine.

Illustrative examples of the mixed amines include dimethylethylamine,methylethylpropylamine, benzylamine, phenethylamine, andbenzyldimethylamine.

Illustrative examples of the aromatic amines and the heterocyclic aminesinclude aniline derivatives (e.g., aniline, N-methylaniline,N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline,3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, andN,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine,triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazolederivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g.,thiazole and isothiazole), imidazole derivatives (e.g., imidazole,4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazolederivatives, furazan derivatives, pyrroline derivatives (e.g., pyrrolineand 2-methyl-1-pyrroline), pyrrolidine derivatives (e.g, pyrrolidine,N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone),imidazoline derivatives, imidazolidine derivatives, pyridine derivatives(e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine,butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine,trimethylpyridine, triethylpyridine, phenylpyridine,3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine,benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine,2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine),pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives,pirazoline derivatives, pyrazolidine derivatives, piperidinederivatives, piperazine derivatives, morpholine derivatives, indolederivatives, isoindole derivatives, 1H-indazole derivatives, indolinederivatives, quinoline derivatives (e.g., quinoline and3-quinolinecarbonitrile), isoquinoline derivatives, cinnolinederivatives, quinazoline derivatives, quinoxaline derivatives,phthalazine derivatives, purine derivatives, pteridine derivatives,carbazole derivatives, phenanthridine derivatives, acridine derivatives,phenazine derivatives, 1,10-phenanthroline derivatives, adeninederivatives, adenosine derivatives, guanine derivatives, guanosinederivatives, uracil derivatives, and uridine derivatives.

Illustrative examples of the nitrogen-containing compound having acarboxyl group include amino benzoic acid, indole carboxylic acid, andamino acid derivatives (e.g., nicotinic acid, alanine, arginine,aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine,3-aminopyrazine-2-carboxylic acid, and methoxy alanine).

Illustrative examples of the nitrogen-containing compound having asulfonyl group include 3-pyridinesulfonic acid and pyridiniump-toluenesulfonate.

Illustrative examples of the nitrogen-containing compound having ahydroxyl group, the nitrogen-containing compound having a hydroxyphenylgroup, and the nitrogen-containing alcoholic compound include 2-hydroxypyridine, amino cresol, 2,4-quinoline diol, 3-indole methanol hydrate,monoethanol amine, diethanol amine, triethanol amine, N-ethyl diethanolamine, N,N-diethyl ethanol amine, triisopropanol amine, 2,2′-iminodiethanol, 2-amino ethanol, 3-amino-1-propanol, 4-amino-1-butanol,4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine,1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine,piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine,1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propane diol,3-pyrrolidino-1,2-propane diol, 8-hydroxyjulolidine, 3-quinuclidinol,3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol,N-(2-hydroxyethyl)-phthalimide, and N-(2-hydroxyethyl)isonicotine amide.

Illustrative examples of the amide derivative include formamide,N-methyl formamide, N,N-dimethyl formamide, acetamide, N-methylacetamide, N,N-dimethyl acetamide, propione amide, and benzamide.

Illustrative examples of the imide derivative include phthalimide,succinimide, and maleimide.

Illustrative examples of the compound shown by the general formula (28)include tris[2-(methoxymethoxy)ethyl]amine,tris[2-(2-methoxyethoxy)ethyl]amine,tris[2-(2-methoxyethoxymethoxy)ethyl]amine,tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy) ethyl]amine,tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane,1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane,1-aza-12-crown-4,1-aza-15-crown-5,1-aza-18-crown-6,tris(2-formyloxyethyl) amine, tris(2-acetoxyethyl) amine,tris(2-propionyloxyethyl) amine, tris(2-butyryloxyethyl) amine,tris(2-isobutyryloxyethyl) amine, tris(2-valeryloxyethyl) amine,tris(2-pivaloyloxyethyl) amine, N,N-bis(2-acetoxyethyl)2-(acetoxyacetoxy)ethyl amine, tris(2-methoxycarbonyloxyethyl) amine,tris(2-tert-butoxycarbonyloxyethyl) amine,tris[2-(2-oxopropoxy)ethyl]amine,tris[2-(methoxycarbonylmethyl)oxyethyl]amine,tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine,tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine,tris(2-methoxycarbonylethyl) amine, tris(2-ethoxycarbonylethyl) amine,N,N-bis(2-hydroxyethyl) 2-(methoxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(methoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-(ethoxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(ethoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-(2-methoxyethoxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(2-methoxyethoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-(2-hydroxyethoxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(2-acetoxyethoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-[(methoxycarbonyl)methoxycarbonyl]ethyl amine,N,N-bis(2-acetoxyethyl) 2-[(methoxycarbonyl)methoxycarbonyl]ethyl amine,N,N-bis(2-hydroxyethyl) 2-(2-oxopropoxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(2-oxopropoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-(tetrahydrofurfuryloxycarbonyl)ethyl amine,N,N-bis(2-acetoxyethyl) 2-(tetrahydrofurfuryloxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethyl amine,N,N-bis(2-hydroxyethyl) 2-(4-hydroxybutoxycarbonyl)ethyl amine,N,N-bis(2-formyloxyethyl) 2-(4-formyloxybutoxycarbonyl)ethyl amine,N,N-bis(2-formyloxyethyl) 2-(2-formyloxyethoxycarbonyl)ethyl amine,N,N-bis(2-methoxyethyl) 2-(methoxycarbonyl)ethyl amine,N-(2-hydroxyethyl) bis[2-(methoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl) bis[2-(methoxycarbonyl)ethyl]amine,N-(2-hydroxyethyl) bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methyl bis(2-acetoxyethyl)amine, N-ethyl bis(2-acetoxyethyl) amine, N-methylbis(2-pivaloyloxyethyl) amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl) amine, N-butylbis(methoxycarbonylmethyl) amine, N-hexyl bis(methoxycarbonylmethyl)amine, and β-(diethylamino)-δ-valerolactone; however, the compound isnot restricted to them.

The above-mentioned basic compounds may be used solely or as a mixtureof two or more kinds.

In view of sensitivity, the amount of the basic compound to be blendedis preferably in the range of 0 to 3 parts by mass, particularlypreferably 0.01 to 1 part by mass, based on 100 parts by mass of (A) thesilicone skeleton-containing polymer compound.

In addition to the components (A) to (E), other additives may be addedto the chemically amplified negative resist composition of the presentinvention. The additives may be exemplified by a surfactant which iscommonly used to enhance coating properties, a light absorber which iscommonly used to enhance light absorption of the photosensitive acidgenerator, and so forth.

As the surfactant, nonionic type surfactants such as fluorinatedsurfactants are preferred, and illustrative examples thereof includeperfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester,perfluoroalkylamine oxide, and a fluorine-containing organosiloxanecompound.

These surfactants may be commercially available products, andillustrative examples thereof include Flolade “FC-4430” (available fromSumitomo 3M Ltd.), Surflon “S-141” and “S-145” (both are available fromAsahi Glass Co., Ltd.), Unidyne “DS-401”, “DS-4031”, and “DS-451” (allare available from Daikin Industries, Ltd.), Megafac “F-8151” (availablefrom DIC Co.), and “X-70-093” (available from Shin-Etsu Chemical Co.,Ltd.). Among them, Flolade “FC-4430” (available from Sumitomo 3M Ltd.)and “X-70-093” (available from Shin-Etsu Chemical Co., Ltd.) arepreferred.

Illustrative examples of the light absorber include diarylsulfoxide,diarylsulfone, 9,10-dimethylanthracene, and 9-fluorenone.

The chemically amplified negative resist composition of the presentinvention may be prepared by a usual method. After the above-mentionedcomponents are mixed by stirring, the resulting mixture is filteredthrough a filter or the like to prepare the chemically amplifiednegative resist composition. Similarly, a later-described photo-curabledry film may be prepared by using this chemically amplified negativeresist composition.

The patterning using the chemically amplified negative resistcomposition of the present invention thus prepared may be performed by awell-known lithography technology. For example, a pattern can be formedby a method including:

(1) applying the above-mentioned chemically amplified negative resistcomposition onto a substrate to form a photosensitive material film;

(2) exposing the photosensitive material film to a high energy beamhaving a wavelength of 190 to 500 nm or an electron beam via a photomaskafter a heat treatment; and

(3) subjecting to development by using an alkaline aqueous solution oran organic solvent as a developer after a heat treatment.

Specifically, the chemically amplified negative resist composition isapplied by a spin coating method onto a silicon wafer, a SiO₂ substrate,a SiN substrate, or a substrate formed with a pattern of a copper wiringor the like, and then, it is prebaked at 80 to 130° C. for 50 to 600seconds approximately to form a resist film having a thickness of 1 to50 μm, preferably 1 to 30 μm, more preferably 5 to 20 μm.

In the spin coating method, after about 5 mL of the resist compositionis dispensed on a silicon substrate, the substrate is rotated, wherebythe resist composition may be applied onto the substrate. By adjustingthe rotation speed during this operation, film thickness of the resistfilm on the substrate can be readily controlled.

Next, a mask to form an intended pattern is put over the resist film,and then, a high energy beam having wavelength of 190 to 500 nm such asi-beam and g-beam is irradiated thereto with an exposure dose of about 1to 5,000 mJ/cm², preferably about 100 to 2,000 mJ/cm². By this exposure,the exposed part is crosslinked to form a pattern not soluble in alater-described developer.

Then, if necessary, post-exposure bake (PEB) may be carried out on a hotplate at a temperature of 60 to 150° C. for a time of 1 to 10 minutes,preferably at 80 to 120° C. for 1 to 5 minutes.

Thereafter, development is carried out by using an aqueous alkalinesolution or an organic solvent as a developer. As to the developer, a2.38% TMAH aqueous solution and the above-mentioned solvent that is usedfor preparing the chemically amplified negative resist composition ofthe present invention may be used. Preferable examples thereof includealcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone,and glycols such as propylene glycol monomethyl ether. The developmentcan be carried out by a usual method, for example, by soaking thesubstrate formed with a pattern into a developer. Then, if necessary,washing, rinsing, drying, and so forth may be performed to obtain aresist film having an intended pattern. Meanwhile, in the case thatpatterning is not necessary, for example, in the case that a uniformfilm is merely wanted, the same procedure as the above-mentionedpatterning process except using no photomask may be employed.

The obtained pattern in the resist film is preferably post-cured byusing an oven or a hot plate at a temperature ranging from 100 to 250°C., preferably from 150 to 220° C., more preferably from 170 to 190° C.If the post-cure temperature is from 100 to 250° C., the crosslinkingdensity of the resist film is increased, and remaining volatilecomponents can be removed. Thus, this temperature range is preferable inview of adhesiveness to a substrate, heat resistance, strength, andelectronic characteristics. The time for the post-cure can be from 10minutes to 10 hours.

The cured film thus obtained has excellent flexibility, adhesiveness toa substrate, heat resistance, electric characteristics, mechanicalstrength, and chemical resistance to a soldering flux liquid, and thus,a semiconductor device having the cured film like this as a top coat hassuperior reliability, and especially, generation of a crack during athermal cycle test can be prevented. In other words, the chemicallyamplified negative resist composition of the present invention canprovide a top coat suitable to protect electric and electronic parts, asemiconductor device, and the like.

(Photo-Curable Dry Film)

Further, the present invention provides a photo-curable dry filmproduced by using the above-mentioned chemically amplified negativeresist composition.

First, the structure of the photo-curable dry film of the presentinvention will be described. The photo-curable dry film has a structurethat a photo-curable resin layer is sandwiched between a supporting filmand a top coat film. For the photo-curable resin layer, the chemicallyamplified negative resist composition of the present invention, which iseffective to form a top coat to protect electric and electronic parts,is used. Such a photo-curable dry film can form a fine pattern in wideranges of film thickness and wavelength, and can be post-cured at lowtemperature to give a top coat having excellent flexibility, heatresistance, electric characteristics, adhesiveness, reliability, andchemical resistance.

In the present invention, the photo-curable resin layer of thephoto-curable dry film obtained from the above-mentioned chemicallyamplified negative resist composition is a solid, so that thephoto-curable resin layer does not contain a solvent. Therefore, thereis no fear that bubbles due to the evaporation remain inside thephoto-curable resin layer as well as between the photo-curable resinlayer and the substrate having concavity and convexity.

The interlayer insulating film is tending to become thinner as asemiconductor device progresses toward downsizing, thinning, andlayer-increasing; however, in view of planarity and step coverage of thesubstrate having concavity and convexity, there is preferable range ofthe film thickness. That is, the film thickness of the photo-curableresin layer is preferably in the range of 10 to 100 μm, more preferably10 to 70 μm, particularly preferably 10 to 50 μm, in view of planarityand step coverage.

In the photo-curable resin layer, viscosity and fluidity are closelyinterrelated. Thus, the photo-curable resin layer can expressappropriate fluidity in the appropriate range of viscosity, and it canpenetrate deep into a narrow space. Accordingly, when the photo-curabledry film having the photo-curable resin layer formed of the chemicallyamplified negative resist composition containing the siliconeskeleton-containing polymer compound of the present invention with anappropriate viscosity as mentioned above adheres to a substrate havingconcavity and convexity, the photo-curable resin layer can cover thesubstrate in accordance with the concavity and the convexity, therebyachieving a high flatness. Moreover, the silicone skeleton-containingpolymer compound, which is a main component of the photo-curable resinlayer, contains a siloxane chain; and because of this, the surfacetension thereof is so low that a higher flatness may be achievable. Inaddition, if the photo-curable resin layer adheres to the substrateunder a vacuum environment, generation of a void therebetween can bemore effectively prevented.

Further, the photo-curable dry film of the present invention can beproduced by a method including:

(I) continuously applying the above-mentioned chemically amplifiednegative resist composition onto a supporting film to form aphoto-curable resin layer,

(II) continuously drying the photo-curable resin layer, and further

(III) laminating a top coat film onto the photo-curable resin layer.

Hereinafter, the inventive method for producing a photo-curable dry filmwill be described more specifically.

In the photo-curable dry film of the present invention, the chemicallyamplified negative resist composition used for forming the photo-curableresin layer is obtained by mixing the components with stirring, followedby filtration through a filter or the like, as mentioned above. Thischemically amplified negative resist composition can be used as amaterial for forming the photo-curable resin layer.

The supporting film used in the photo-curable dry film of the presentinvention may be a monolayer or a multilayer film having plural polymerfilms being laminated. The material thereof may be exemplified by asynthetic resin film such as polyethylene, polypropylene, polycarbonate,and polyethylene terephthalate, etc. Among these, polyethyleneterephthalate is preferable because it has appropriate flexibility,mechanical strength, and heat resistance. These films may be variouslysubjected to, for example, corona treatment and coating treatment with areleasing agent. For this, many commercial films may be used.Illustrative examples thereof include Cerapeel WZ (RX) and Cerapeel BX8(R) (both are available from Toray Advanced Film Co., Ltd.), E7302 andE7304 (both are available from Toyobo Co., Ltd.), Purex G31 and PurexG71T1 (both are available from Teijin DuPont Films Japan Ltd.), andPET38×1-A3, PET38×1-V8, and PET38×1-X08 (all available from Nippa Co.,Ltd.).

The top coat film used in the photo-curable dry film of the presentinvention may be the same film as the above-mentioned supporting film,but polyethylene terephthalate and polyethylene having appropriateflexibility are preferred. For this, commercial films may be used, andillustrative examples thereof include, besides the polyethyleneterephthalates that have already been mentioned, polyethylene such asGF-8 (available from Tamapoly Co., Ltd.) and PE Film 0-Type (availablefrom Nippa Co., Ltd.).

The thicknesses of the supporting film and the top coat film arepreferably both in the range of 10 to 100 μm, particularly preferably 25to 50 μm, in view of stable production of the photo-curable dry film andthe rolling habit around a roll axis, so-called curl-prevention.

As to the manufacturing equipment for the photo-curable dry film, a filmcoater that is generally used for producing an adhesive product may beused. Illustrative examples of the film coater include a comma coater, acomma reverse coater, a multi coater, a die coater, a lip coater, a lipreverse coater, a direct gravure coater, an offset gravure coater, a3-roll bottom reverse coater, and a 4-roll bottom reverse coater.

The supporting film is rolled-out from a roll-out axis of the filmcoater; and the chemically amplified negative resist composition iscontinuously applied onto the supporting film with a prescribedthickness to form the photo-curable resin layer while it is passingthrough a coater head of the film coater; and then, after it is passedthrough a hot-air circulating oven at a prescribed temperature for aprescribed period, the photo-curable resin layer that has beencontinuously dried on the supporting film is passed through a laminateroll together with the top coat film that has been rolled-out fromanother roll-out axis of the film coater under a prescribed pressure,thereby bonding the top coat film to the photo-curable resin layer onthe supporting film, followed by roll-up to a roll-up axis of the filmcoater. In this case, temperature of the hot-air circulating oven ispreferably in the range of 25 to 150° C., the period for passing throughit is preferably in the range of 1 to 100 minutes, and the laminate rollpressure is preferably in the range of 0.01 to 5 MPa.

Further, a pattern can be formed by using the photo-curable dry filmthus produced. For example, a pattern can be formed by a methodincluding:

(i) separating the top coat film from the above-mentioned photo-curabledry film and bringing an exposed photo-curable resin layer into closecontact with a substrate;

(ii) exposing the photo-curable resin layer to a high energy beam havinga wavelength of 190 to 500 nm or an electron beam via a photomask eitherthrough the supporting film or in a peeled-off state of the supportingfilm;

(iii) subjecting to a heat treatment after the exposure; and

(iv) subjecting to development by using an alkaline aqueous solution oran organic solvent as a developer.

Hereinafter, the patterning process using the photo-curable dry film ofthe present invention will be described more specifically.

In the patterning process using the photo-curable dry film of thepresent invention, first, the top coat film is delaminated from thephoto-curable dry film to bring the photo-curable resin layer into closecontact with the substrate. Then, photo exposure is performed, followedby post-exposure bake (hereinafter, PEB). Subsequently, development isperformed, and if necessary, post-curing is carried out, whereby a curedfilm formed with a pattern can be obtained.

First, the photo-curable dry film is brought into close contact with asubstrate by using a film adhering equipment. The substrate may beexemplified by a silicon wafer, a silicon wafer for TSV, a circuitsubstrate made of plastics, ceramics, various metals, etc., andespecially, the substrate having a trench or a hole with an aperturewidth of 10 to 100 μm and a depth of 10 to 120 μm may be mentioned. Asto the film adhering equipment, a vacuum laminator is preferred.

Specifically, the photo-curable dry film is attached to a film adheringequipment, the top coat film of the photo-curable dry film isdelaminated, and the photo-curable resin layer thereby exposed isbrought into close contact with a substrate on a table at a prescribedtemperature by using an adhering roll under a prescribed pressure in avacuum chamber with a prescribed degree of vacuum. Meanwhile,temperature of the table is preferably in the range of 60 to 120° C.,pressure of the adhering roll is preferably in the range of 0 to 5.0MPa, and degree of vacuum in the vacuum chamber is preferably in therange of 50 to 500 Pa.

After close contact, patterning may be performed by using a well-knownlithography technology. At this time, if necessary, pre-bake may becarried out in order to effectively carry out the photo-curing reactionof the photo-curable resin layer as well as to enhance the adhesivenessbetween the photo-curable resin layer and the substrate. The pre-bakemay be carried out, for example, at 40 to 140° C. for 1 minute to 1 hourapproximately.

Then, curing is carried out by exposure to a light having a wavelengthof 190 to 500 nm via a photomask under the state of intervention of thesupporting film or under the state of the supporting film delaminated.The photomask may be obtained by engraving a prescribed pattern.Meanwhile, the photomask is preferably made of a material that canshield the light having a wavelength of 190 to 500 nm. For example,chromium and the like are preferably used, but it is not limitedthereto.

As to the light having a wavelength of 190 to 500 nm, lights havingvarious wavelengths generated from, for example, a radiation-beamgenerating instrument may be used. Illustrative examples thereof includeUV light such as g-beam and i-beam, and far ultraviolet light (248 nmand 193 nm). The wavelength is preferably in the range of 248 to 436 nm.The exposure dose is preferably, for example, in the range of 10 to3,000 mJ/cm². By subjecting to the exposure as mentioned above, theexposed part is crosslinked to form the pattern not soluble in thedeveloper (this will be mentioned later).

Then, post-exposure bake (PEB) is carried out to enhance the developmentsensitivity. The post-exposure baking may be performed, for example, at40 to 140° C. for 0.5 to 10 minutes.

Thereafter, development is carried out by using an aqueous alkalinesolution or an organic solvent as a developer. As to the developer, a2.38% TMAH aqueous solution and the above-mentioned solvent that is usedfor preparing the chemically amplified negative resist composition usedfor forming the photo-curable resin layer of the photo-curable dry filmof the present invention may be used. Preferable examples thereofinclude alcohols such as isopropyl alcohol (IPA), ketones such ascyclohexanone, and glycols such as propylene glycol monomethyl ether.The development can be carried out by a usual method, for example, bysoaking the substrate formed with a pattern into a developer. Then, ifnecessary, washing, rinsing, drying, and so forth may be performed toobtain a film of the photo-curable resin layer having an intendedpattern. Meanwhile, in the case that patterning is not necessary, forexample, in the case that a uniform film is merely wanted, the sameprocedure as the above-mentioned patterning process except using nophotomask may be employed.

The obtained pattern may be post-cured by using an oven or a hot plateat a temperature ranging from 100 to 250° C., preferably from 150 to220° C., more preferably from 170 to 190° C. If the post-curetemperature is from 100 to 250° C., the crosslinking density of the filmof the photo-curable resin layer is increased, and remaining volatilecomponents can be removed. Thus, this temperature range is preferable inview of adhesiveness to a substrate, heat resistance, strength, andelectronic characteristics. The time for the post-cure can be from 10minutes to 10 hours.

The cured film thus obtained has excellent flexibility, adhesiveness toa substrate, heat resistance, electric characteristics, mechanicalstrength, and chemical resistance to a soldering flux liquid; and thus,a semiconductor device having the cured film like this as a top coat hassuperior reliability, and especially, generation of a crack during athermal cycle test can be prevented. In other words, the photo-curabledry film of the present invention can provide a top coat suitable toprotect electric and electronic parts, a semiconductor device, and thelike.

In this way, the photo-curable dry film of the present invention can beeffectively applied to the substrate having a trench or a hole. Thus,the present invention provides a layered product that has a substrateincluding a trench and/or a hole each having an aperture width of 10 to100 μm and a depth of 10 to 120 μm, and a cured layer of thephoto-curable resin formed of the photo-curable dry film laminated onthe substrate.

In addition, the present invention provides a substrate that isprotected by a film obtained by curing a pattern formed by theabove-mentioned patterning process.

Further, the present invention provides a semiconductor apparatus thathas a film obtained by curing a pattern formed by the above-mentionedpatterning process.

As mentioned above, the chemically amplified negative resist compositionof the present invention and the photo-curable dry film produced byusing this composition can give a top coat having excellent flexibility,adhesiveness to a substrate, heat resistance, electric characteristics,mechanical strength, and chemical resistance by curing themselves. Thus,these are useful to an insulating film for a semiconductor deviceincluding a rewiring use, an insulating film for a multilayer printedsubstrate, a solder mask, a cover lay film, and an insulating film forembedding a through-silicon via (TSV) as well as useful for bonding to asubstrate.

EXAMPLES

Hereinafter, the present invention is explained in more detail byreferring to Synthesis Examples and Examples, but the present inventionis not limited to the following examples. Meanwhile, in the followingexamples, the term “parts” indicates parts by mass.

I. Preparation of Chemically Amplified Negative Resist Composition

The structures of compounds (M-1) to (M-12) used in Synthesis Examplesare shown below.

The silicone skeleton-containing polymer compound having a repeatingunit shown by the general formula (3) of the present invention is shownbelow,

wherein R¹ to R⁶, “l”, “m”, “a”, “b”, “c”, “d”, “e”, “f”, “g”, “h”, “i”,“j”, X, Y, W, U, and T each are as defined above.

[Synthesis Example 1] Synthesis of4,4-bis(4-hydroxy-3-allylphenyl)pentanol (M-1)

A 5-L flask equipped with a stirrer, thermometer, and nitrogen purgesystem was charged with 458 g of diphenolic acid, 884 g of potassiumcarbonate, and 2,000 g of dimethylacetamide. Then, 774 g of allylbromidewas added dropwise thereto while stirring at room temperature undernitrogen atmosphere, followed by further stirring at 60° C. for 58hours. To the resulting mixture was added dropwise 221 g of potassiumthe temperature, and the mixture was further stirred at 60° C. for 20hours. After 2,000 g of water was added dropwise under ice-cooling toterminate the reaction, 1,000 g of toluene, 1,000 g of hexane, 2,000 gof water were added, and the organic layer was collected. The obtainedorganic layer was successively washed with 2,000 g of water, 500 g ofwater four times, and 500 g of saturated saline, and the solvent wasdistilled off to obtain 686 g of a crude material of allyl4,4-bis(4-allyloxyphenyl)pentanoate.

A 5-L flask equipped with a stirrer, thermometer, and nitrogen purgesystem under nitrogen atmosphere was charged with 655 g of the allyl4,4-bis(4-allyloxy-phenyl)pentanoate and 1,310 g of tetrahydrofuran tomake a solution. Then, 605 g of sodium bis(2-methoxyethoxy)aluminumhydride (70% by mass of toluene solution) was added dropwise theretounder ice-cooling. After stirring at room temperature for 3 hours, 1,526g of 10% by mass hydrochloric acid was added dropwise under ice-coolingto terminate the reaction. To the reaction solution was added 250 g ofethyl acetate and 750 g of toluene, and the organic layer was collectedand washed 3 times with 500 g of water. The solvent of the obtainedorganic layer was distilled off, and the remainder was dissolved in1,000 g of toluene, and washed with 300 g of 4% by mass aqueous sodiumhydroxide solution 5 times, 330 g of 2% by mass hydrochloric acid, andthen 300 g of water 4 times. Thereafter, the solvent of the obtainedorganic layer was distilled off to obtain 555 g of a crude material of4,4-bis(4-allyloxyphenyl)pentanol.

Then, a 5-L flask equipped with a stirrer, thermometer, and nitrogenpurge system under nitrogen atmosphere was charged with 500 g of the4,4-bis(4-allyloxyphenyl)pentanol and 500 g of N,N-diethylaniline tomake a solution, and the solution was heated at 180° C. and stirred for18 hours. After cooled to room temperature, 1,460 g of 10% by masshydrochloric acid was added dropwise under ice-cooling, and 2,400 g ofethyl acetate was added to the reaction mixture. Then, the organic layerwas collected and washed 4 times with 2,400 g of water. The solvent ofthe obtained organic layer was distilled off, and the remainder wasdissolved in 500 g of ethyl acetate, and 2,000 g of hexane was addeddropwise thereto under stirring. Thereafter, the hexane layer wasremoved, and the remaining oily material was dissolved in 500 g of ethylacetate and collected. Then, the solvent of the obtained organic layerwas distilled off, thereby obtaining 466 g of4,4-bis(4-hydroxy-3-allylphenyl)pentanol (M-1) with a yield of 93%.Incidentally, the compound (M-1) was identified by ¹H-NMR (600 MHz)(JEOL-600 spectrometer manufactured by JEOL, Ltd.).

[Synthesis Example 2] Synthesis ofbis(4-hydroxy-3-allylphenyl)-(4-hydroxyphenyl)-methane (M-2)

A 3-necked 1-L flask inside which was replaced with nitrogen was chargedwith 50.0 g (409 mmol) of 4-hydroxybenzaldehyde and 330.0 g (2,457 mmol)of 2-allylphenol. The mixture was stirred at room temperature todissolve the 4-hydroxybenzaldehyde, and transferred to an ice bath.Then, 7.9 g of methanesulfonic acid was added dropwise slowly whilemaintaining the reaction solution at 10° C. or lower. After dropwiseaddition, the reaction solution was aged for 10 hours at roomtemperature, and 400 g of toluene and 400 g of saturated sodium hydrogencarbonate in aqueous solution were added thereto, and this mixture wastransferred to a 2-L separatory funnel. The aqueous layer was removedtherefrom, and 400 g of saturated sodium hydrogen carbonate in aqueoussolution was added thereto for liquid separation followed bywater-washing with 400 g of ultrapure water twice. After the collectedorganic layer was crystallized by 4,400 g of hexane, supernatant wasremoved, and the remainder was dissolved in 300 g of toluene tocrystallize again by 2,000 g of hexane. This procedure was repeated onceagain, and the precipitated crystal was collected by filtration anddried, thereby obtaining 95 g ofbis(4-hydroxy-3-allylphenyl)-(4-hydroxyphenyl)-methane (M-2) with ayield of 58%. Incidentally, the compound (M-2) was identified by ¹H-NMR(600 MHz) (JEOL-600 spectrometer manufactured by JEOL, Ltd.).

[Synthesis Example 3] Synthesis of Compound (M-12)

A 3-necked 1-L flask inside which was replaced with nitrogen was chargedwith 348 g (3.28 mol) of dimethoxymethylsilane and 2.1 g of toluenesolution containing chloroplatinic acid (5% by mass), followed byheating at 60° C. Then, 400 g (2.98 mol) of 4-methoxystyrene was addeddropwise thereto over 7 hours. At this time, the heating temperature wasincreased up to 100° C. as the reaction system temperature rose. Afterdropwise addition, the mixture was cooled to room temperature, andpurified by distillation to obtain 583 g of compound (M-12) with a yieldof 81.4%. Incidentally, the compound (M-12) was identified by ¹H-NMR(600 MHz) (JEOL-600 spectrometer manufactured by JEOL, Ltd.).

[Synthesis Example 4] Synthesis of Compound (M-9)

A 3-necked 1-L flask was charged with 212 g of the compound (M-12); and162 g of 7.5% by mass aqueous potassium hydroxide solution was addedthereto under stirring at room temperature. After addition, the mixturewas heated at 100° C., and aged for 6 hours while removing generatedmethanol from the system. Then, the mixture was cooled to roomtemperature, and 200 g of toluene and 68 g of 10% by mass hydrochloricacid were added. This mixture was transferred to a 1-L separatoryfunnel, and the lower aqueous layer was removed. Further, liquidseparation and water-washing was repeated 3 times with 50 g of ultrapurewater, and the organic layer was concentrated under reduced pressure toobtain 166 g of hydrolysis condensate of the compound (M-12).

A 3-necked 1-L flask inside which was replaced with nitrogen was chargedwith 164 g of the obtained hydrolysis condensate (0.84 mol when assumingthat one condensation unit corresponds to its molecular weight), 125 gof cyclic tetramer of dimethylsiloxane (1.69 mol when assuming that onecondensation unit corresponds to its molecular weight), and 37.4 g (0.28mol) of 1,1,3,3-tetramethyldisiloxane; and the mixture was stirred atroom temperature. Then, 1.5 g of trifluoromethanesulfonic acid was addeddropwise thereto under stirring, and after dropwise addition, themixture was heated at 60° C., and aged for 3 hours. The mixture was thencooled to room temperature, and 300 g of toluene and 208 g of 4% by massaqueous sodium hydrogencarbonate solution were added thereto, followedby stirring for 1 hour. This mixture was transferred to a 1-L separatoryfunnel, and the lower aqueous layer was removed. Further, liquidseparation and water-washing was repeated twice with 200 g of ultrapurewater, and the organic layer was concentrated under reduced pressure toobtain compound (M-9). Incidentally, the compound (M-9) was identifiedby ¹H-NMR (600 MHz) (JEOL-600 spectrometer manufactured by JEOL, Ltd.).

[Synthesis Example 5] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-1)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 350 g of toluene and 120 g ofcompound (M-1) to make a solution. To the solution were added 58 g ofcompound (M-3) and 84 g of compound (M-7), and the resulting mixture washeated at 60° C. Thereafter, 1.1 g of carbon carried platinum catalyst(5% by mass) was added thereto, and the mixture was heated at 90° C. andaged for 3 hours. Then, the mixture was cooled to 60° C., 1.1 g ofcarbon carried platinum catalyst (5% by mass) was added again, and 62 gof compound (M-11) was dropped into the flask over 30 minutes. At thistime, the temperature inside the flask was increased to 65 to 67° C.After dropwise addition, the mixture was further aged at 90° C. for 3hours, and cooled to room temperature. Then, 780 g of methyl isobutylketone was added to the reaction solution, and this reaction solutionwas filtered under pressure through a filter to remove the platinumcatalyst. Further, to the obtained solution containing a siliconeskeleton-containing polymer compound was added 780 g of pure water, andthe mixture was stirred, allowed to stand, and separated to remove thelower aqueous layer. This liquid separation and water-washing operationwas repeated 6 times to remove trace amounts of acid component in thesilicone skeleton-containing polymer compound solution. The solvent inthe resulting silicone skeleton-containing polymer compound solution wasdistilled off under reduced pressure and instead, 750 g oftetrahydrofuran was added thereto, and the tetrahydrofuran solution wasconcentrated under reduced pressure so as to have a solid concentrationof 30% by mass, thereby obtaining a solution containing siliconeskeleton-containing polymer compound (A-1) and tetrahydrofuran as themain solvent. The molecular weight of the silicone skeleton-containingpolymer compound in this solution was measured by GPC, consequentlyfinding a weight average molecular weight of 10,000 in terms ofpolystyrene. The polymer compound corresponds to the general formula (3)wherein a=0, b=0, c=0, d=0, e=0.513, f=0.187, g=0, h=0, i=0.220,j=0.080, and W and T are as follows.

[Synthesis Example 6] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-2)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 497 g of toluene and 120 g ofcompound (M-1) to make a solution. To the solution were added 136 g ofcompound (M-3) and 119 g of compound (M-7), and the resulting mixturewas heated at 60° C. Thereafter, 1.6 g of carbon carried platinumcatalyst (5% by mass) was added thereto, and the mixture was heated at90° C. and aged for 3 hours. Then, the mixture was cooled to 60° C., 1.6g of carbon carried platinum catalyst (5% by mass) was added again, and87 g of compound (M-11) was dropped into the flask over 30 minutes. Atthis time, the temperature inside the flask was increased to 65 to 67°C. After dropwise addition, the mixture was further aged at 90° C. for 3hours, and cooled to room temperature. Then, 780 g of methyl isobutylketone was added to the reaction solution, and this reaction solutionwas filtered under pressure through a filter to remove the platinumcatalyst. Further, to the obtained solution containing a siliconeskeleton-containing polymer compound was added 780 g of pure water, andthe mixture was stirred, allowed to stand, and separated to remove thelower aqueous layer. This liquid separation and water-washing operationwas repeated 6 times to remove trace amounts of acid component in thesilicone skeleton-containing polymer compound solution. The solvent inthe resulting silicone skeleton-containing polymer compound solution wasdistilled off under reduced pressure and instead, 1,078 g oftetrahydrofuran was added thereto, and the tetrahydrofuran solution wasconcentrated under reduced pressure so as to have a solid concentrationof 30% by mass, thereby obtaining a solution containing siliconeskeleton-containing polymer compound (A-2) and tetrahydrofuran as themain solvent. The molecular weight of the silicone skeleton-containingpolymer compound in this solution was measured by GPC, consequentlyfinding a weight average molecular weight of 13,000 in terms ofpolystyrene. The polymer compound corresponds to the general formula (3)wherein a=0, b=0, c=0, d=0, e=0.367, f=0.133, g=0, h=0, i=0.367,j=0.133, and W and T are as follows.

[Synthesis Example 7] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-3)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 5 except that 362 g of compound(M-8) was used in place of 84 g of compound (M-7), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-3). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 30,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0, b=0, c=0, d=0,e=0.513, f=0.187, g=0, h=0, i=0.220, j=0.080, and W and T are asfollows.

[Synthesis Example 8] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-4)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 5 except that 188 g of compound(M-9) was used in place of 84 g of compound (M-7), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-4). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 26,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0, b=0, c=0, d=0,e=0.513, f=0.187, g=0, h=0, i=0.220, j=0.080, and W and T are asfollows.

[Synthesis Example 9] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-5)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 5 except that 141 g of compound(M-10) was used in place of 84 g of compound (M-7), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-5). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 10,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0, b=0, c=0, d=0,e=0.513, f=0.187, g=0, h=0, i=0.220, j=0.080, and W and T are asfollows.

[Synthesis Example 10] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-6)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 411 g of toluene and 120 g ofcompound (M-1) to make a solution. To the solution were added 68 g ofcompound (M-3), 24 g of compound (M-4), and 219 g of compound (M-9), andthe resulting mixture was heated at 60° C. Thereafter, 1.3 g of carboncarried platinum catalyst (5% by mass) was added thereto, and themixture was heated at 90° C. and aged for 3 hours. Then, the mixture wascooled to 60° C., 1.3 g of carbon carried platinum catalyst (5% by mass)was added again, and 73 g of compound (M-11) was dropped into the flaskover 30 minutes. At this time, the temperature inside the flask wasincreased to 65 to 67° C. After dropwise addition, the mixture wasfurther aged at 90° C. for 3 hours, and cooled to room temperature.Then, 780 g of methyl isobutyl ketone was added to the reactionsolution, and this reaction solution was filtered under pressure througha filter to remove the platinum catalyst. Further, to the obtainedsolution containing a silicone skeleton-containing polymer compound wasadded 780 g of pure water, and the mixture was stirred, allowed tostand, and separated to remove the lower aqueous layer. This liquidseparation and water-washing operation was repeated 6 times to removetrace amounts of acid component in the silicone skeleton-containingpolymer compound solution. The solvent in the resulting siliconeskeleton-containing polymer compound solution was distilled off underreduced pressure and instead, 1,050 g of tetrahydrofuran was addedthereto, and the tetrahydrofuran solution was concentrated under reducedpressure so as to have a solid concentration of 30% by mass. Thus, asolution containing silicone skeleton-containing polymer compound (A-6)and tetrahydrofuran as the main solvent was obtained. The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 24,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0.073, b=0.027, c=0,d=0, e=0.440, f=0.160, g=0, h=0, i=0.220, j=0.080, and X, W, and T areas follows.

[Synthesis Example 11] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-7)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 10 except that 17 g of compound(M-5) was used in place of 24 g of compound (M-4), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-7). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 23,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0.073, b=0.027, c=0,d=0, e=0.440, f=0.160, g=0, h=0, i=0.220, j=0.080, and X, W, and T areas follows.

[Synthesis Example 12] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-8)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 10 except that 24 g of compound(M-6) was used in place of 24 g of compound (M-4), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-8). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 23,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0, b=0, c=0.073,d=0.027, e=0.440, f=0.160, g=0, h=0, i=0.220, j=0.080, and Y, W, and Tare as follows.

[Synthesis Example 13] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-9)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 5 except that 131 g of compound(M-2) was used in place of 120 g of compound (M-1), and tetrahydrofuranwas added thereto as the main solvent to obtain a solution containingsilicone skeleton-containing polymer compound (A-9). The molecularweight of the silicone skeleton-containing polymer compound in thissolution was measured by GPC, consequently finding a weight averagemolecular weight of 10,000 in terms of polystyrene. The polymer compoundcorresponds to the general formula (3) wherein a=0, b=0, c=0, d=0,e=0.513, f=0.187, g=0, h=0, i=0.220, j=0.080, and W and T are asfollows.

[Synthesis Example 14] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-10)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 1,000 g of the tetrahydrofuransolution containing 30% by mass of the silicone skeleton-containingpolymer compound (A-1) synthesized in Synthesis Example 5; and 31 g ofsuccinic anhydride and 32 g of triethylamine were added thereto,followed by heating at 50° C. After stirring for 2 hours, the mixturewas cooled to room temperature, and 900 g of saturated aqueous ammoniumchloride solution and 1,500 g of ethyl acetate were added thereto toterminate the reaction. Then, the aqueous layer was removed, and liquidseparation and water-washing was repeated 5 times with 900 g ofultrapure water. The solvent of the collected organic layer wasdistilled off and instead, 600 g of cyclopentanone was added thereto,and the resulting cyclopentanone solution was concentrated under reducedpressure so as to have a solid concentration of 40 to 50% by mass,thereby obtaining a solution containing silicone skeleton-containingpolymer compound having carboxylic acid (A-10) and cyclopentanone as themain solvent. The molecular weight of the silicone skeleton-containingpolymer compound in this solution was measured by GPC, consequentlyfinding a weight average molecular weight of 10,000 in terms ofpolystyrene. The polymer compound corresponds to the general formula (3)wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187, i=0.220,j=0.080, and U and T are as follows.

[Synthesis Example 15] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-11)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,414 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-2) synthesized in SynthesisExample 6 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-11). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 13,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.367, h=0.133,i=0.367, j=0.133, and U and T are as follows.

[Synthesis Example 16] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-12)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,844 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-3) synthesized in SynthesisExample 7 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-12). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 30,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 17] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-13)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,296 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-4) synthesized in SynthesisExample 8 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-13). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 26,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 18] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-14)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,114 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-5) synthesized in SynthesisExample 9 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-14). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 19] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-15)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,525 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-6) synthesized in SynthesisExample 10 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-15). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 24,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0.073, b=0.027, c=0, d=0, e=0, f=0, g=0.440,h=0.160, i=0.220, j=0.080, and X, U, and T are as follows.

[Synthesis Example 20] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-16)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,503 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-7) synthesized in SynthesisExample 11 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-16). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 23,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0.073, b=0.027, c=0, d=0, e=0, f=0, g=0.440,h=0.160, i=0.220, j=0.080, and X, U, and T are as follows.

[Synthesis Example 21] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-17)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,523 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-8) synthesized in SynthesisExample 12 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-17). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 23,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0.073, d=0.027, e=0, f=0, g=0.440,h=0.160, i=0.220, j=0.080, and Y, U, and T are as follows.

[Synthesis Example 22] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-18)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 1,031 g of thetetrahydrofuran solution containing 30% by mass of the siliconeskeleton-containing polymer compound (A-9) synthesized in SynthesisExample 13 was used in place of 1,000 g of the tetrahydrofuran solutioncontaining 30% by mass of the silicone skeleton-containing polymercompound (A-1), and cyclopentanone was added thereto as the main solventto obtain a solution containing silicone skeleton-containing polymercompound (A-18). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 23] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-19)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 48 g ofcyclohexyldicarboxylic anhydride was used in place of 31 g of succinicanhydride, and cyclopentanone was added thereto as the main solvent toobtain a solution containing silicone skeleton-containing polymercompound (A-19). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 24] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-20)

A silicone skeleton-containing polymer compound was synthesized in thesame manner as in Synthesis Example 14 except that 51 g of5-norbornene-2,3-dicarboxylic anhydride was used in place of 31 g ofsuccinic anhydride, and cyclopentanone was added thereto as the mainsolvent to obtain a solution containing silicone skeleton-containingpolymer compound (A-20). The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0, f=0, g=0.513, h=0.187,i=0.220, j=0.080, and U and T are as follows.

[Synthesis Example 25] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-21)

The solvent in the solution containing the silicone skeleton-containingpolymer compound (A-1) and tetrahydrofuran as the main solvent obtainedin Synthesis Example 5 was exchanged with cyclopentanone to obtain asolution containing silicone skeleton-containing polymer compound (A-21)and cyclopentanone with a solid concentration of 40 to 50% by mass asthe main solvent. The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0.513, f=0.187, g=0, h=0,i=0.220, j=0.080, and W and T are as follows.

[Synthesis Example 26] Synthesis of Silicone Skeleton-Containing PolymerCompound (A-22)

The solvent in the solution containing the silicone skeleton-containingpolymer compound (A-9) and tetrahydrofuran as the main solvent obtainedin Synthesis Example 13 was exchanged with cyclopentanone to obtain asolution containing silicone skeleton-containing polymer compound (A-22)and cyclopentanone with a solid concentration of 40 to 50% by mass asthe main solvent. The molecular weight of the siliconeskeleton-containing polymer compound in this solution was measured byGPC, consequently finding a weight average molecular weight of 10,000 interms of polystyrene. The polymer compound corresponds to the generalformula (3) wherein a=0, b=0, c=0, d=0, e=0.513, f=0.187, g=0, h=0,i=0.220, j=0.080, and W and T are as follows.

[Comparative Synthesis Example 1] Synthesis of SiliconeSkeleton-Containing Polymer Compound (B-1)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 350 g of toluene and 120 g ofcompound (M-1) to make a solution. To the solution were added 63 g ofcompound (M-4) and 84 g of compound (M-7), and the resulting mixture washeated at 60° C. Thereafter, 1.1 g of carbon carried platinum catalyst(5% by mass) was added thereto, and the mixture was heated at 90° C. andaged for 3 hours. Then, the mixture was cooled to 60° C., 1.1 g ofcarbon carried platinum catalyst (5% by mass) was added again, and 62 gof compound (M-11) was dropped into the flask over 30 minutes. At thistime, the temperature inside the flask was increased to 65 to 67° C.After dropwise addition, the mixture was further aged at 90° C. for 3hours, and cooled to room temperature. Then, 780 g of methyl isobutylketone was added to the reaction solution, and this reaction solutionwas filtered under pressure through a filter to remove the platinumcatalyst. Further, to the obtained solution containing a siliconeskeleton-containing polymer compound was added 780 g of pure water, andthe mixture was stirred, allowed to stand, and separated to remove thelower aqueous layer. This liquid separation and water-washing operationwas repeated 6 times to remove trace amounts of acid component in thesilicone skeleton-containing polymer compound solution. The solvent inthe resulting silicone skeleton-containing polymer compound solution wasdistilled off under reduced pressure and instead, 750 g oftetrahydrofuran was added thereto, and the tetrahydrofuran solution wasconcentrated under reduced pressure so as to have a solid concentrationof 30% by mass, thereby obtaining a solution containing siliconeskeleton-containing polymer compound (B-1) and tetrahydrofuran as themain solvent. The molecular weight of the silicone skeleton-containingpolymer compound in this solution was measured by GPC, consequentlyfinding a weight average molecular weight of 10,000 in terms ofpolystyrene. The polymer compound corresponds to the general formula (3)wherein a=0.220, b=0.080, c=0, d=0, e=0.513, f=0.187, g=0, h=0, i=0,j=0, and X and W are as follows.

[Comparative Synthesis Example 2] Synthesis of SiliconeSkeleton-Containing Polymer Compound (B-2)

A 3-L flask equipped with a stirrer, thermometer, nitrogen purge system,and reflux condenser was charged with 1,000 g of the tetrahydrofuransolution containing 30% by mass of the silicone skeleton-containingpolymer compound (B-1) synthesized in Comparative Synthesis Example 1;and 31 g of succinic anhydride and 32 g of triethylamine were addedthereto, followed by heating at 50° C. After stirring for 2 hours, themixture was cooled to room temperature, and 900 g of saturated aqueousammonium chloride solution and 1,500 g of ethyl acetate were addedthereto to terminate the reaction. Then, the aqueous layer was removed,and liquid separation and water-washing was repeated 5 times with 900 gof ultrapure water. The solvent of the collected organic layer wasdistilled off and instead, 600 g of cyclopentanone was added thereto,and the resulting cyclopentanone solution was concentrated under reducedpressure so as to have a solid concentration of 40 to 50% by mass,thereby obtaining a solution containing silicone skeleton-containingpolymer compound having carboxylic acid (B-2) and cyclopentanone as themain solvent. The molecular weight of the silicone skeleton-containingpolymer compound in this solution was measured by GPC, consequentlyfinding a weight average molecular weight of 10,000 in terms ofpolystyrene. The polymer compound corresponds to the general formula (3)wherein a=0.220, b=0.080, c=0, d=0, e=0, f=0, g=0.513, h=0.187, i=0,j=0, and X and U are as follows.

The solutions of the silicone skeleton-containing polymer compounds(A-10) to (A-20) synthesized in Synthesis Examples 14 to 24, thesilicone skeleton-containing polymer compound (B-2) synthesized inComparative Synthesis Example 2, and the silicone skeleton-containingpolymer compounds (A-21) and (A-22) synthesized in Synthesis Examples 25and 26 were used. Each of the solutions was blended with a crosslinkingagent, a photosensitive acid generator, a basic compound, andcyclopentanone as an additional solvent, with the composition and theblending ratio shown in Table 1, to prepare a resist composition with aconcentration of 45% by mass in terms of the resin. Thereafter, thecomposition was stirred, mixed, dissolved, and then filtered through a0.5 μm filter made of Teflon (registered trade mark) for microfiltrationto obtain a desired resist composition.

TABLE 1 Silicone skeleton- containing Photo- Cross- polymer sensitivelinking Basic compound acid generator agent compound Resist A-10 PAG-1XL-1 Amine-1 composition 1 (100 parts (1.0 part (10.0 parts (0.2 part bymass) by mass) by mass) by mass) Resist A-11 PAG-1 XL-1 Amine-1composition 2 (100 parts (1.0 part (10.0 parts (0.2 part by mass) bymass) by mass) by mass) Resist A-12 PAG-1 XL-1 Amine-1 composition 3(100 parts (1.0 part (10.0 parts (0.2 part by mass) by mass) by mass) bymass) Resist A-13 PAG-1 XL-1 Amine-1 composition 4 (100 parts (1.0 part(10.0 parts (0.2 part by mass) by mass) by mass) by mass) Resist A-14PAG-1 XL-1 Amine-1 composition 5 (100 parts (1.0 part (10.0 parts (0.2part by mass) by mass) by mass) by mass) Resist A-15 PAG-1 XL-1 Amine-1composition 6 (100 parts (1.0 part (10.0 parts (0.2 part by mass) bymass) by mass) by mass) Resist A-16 PAG-1 XL-1 Amine-1 composition 7(100 parts (1.0 part (10.0 parts (0.2 part by mass) by mass) by mass) bymass) Resist A-17 PAG-1 XL-1 Amine-1 composition 8 (100 parts (1.0 part(10.0 parts (0.2 part by mass) by mass) by mass) by mass) Resist A-18PAG-1 XL-1 Amine-1 composition 9 (100 parts (1.0 part (10.0 parts (0.2part by mass) by mass) by mass) by mass) Resist A-19 PAG-1 XL-1 Amine-1composition 10 (100 parts (1.0 part (10.0 parts (0.2 part by mass) bymass) by mass) by mass) Resist A-20 PAG-1 XL-1 Amine-1 composition 11(100 parts (1.0 part (10.0 parts (0.2 part by mass) by mass) by mass) bymass) Resist B-2 PAG-1 XL-1 Amine-1 composition 12 (100 parts (1.0 part(10.0 parts (0.2 part by mass) by mass) by mass) by mass) Resist A-21PAG-1 XL-1 Amine-1 composition 13 (100 parts (1.0 part (10.0 parts (0.2part by mass) by mass) by mass) by mass) Resist A-22 PAG-1 XL-1 Amine-1composition 14 (100 parts (1.0 part (10.0 parts (0.2 part by mass) bymass) by mass) by mass)

In Table 1, Photosensitive acid generator (PAG-1), Crosslinking agent(XL-1), and Basic compound (Amine-1) are as shown below.

II. Exposure and Pattern Formation

Each of the resist compositions 1 to 12 (5 mL) was dispensed on asilicon substrate, and then the substrate was rotated to apply theresist composition by spin coating so as to give a film thickness of 20μm.

Then, pre-bake was carried out on a hot plate at 100° C. for 2 minutes.Subsequently, this substrate was mounted with a mask capable of forming20 μm holes arranged in 1:1 lengthwise and breadthwise, and exposed to abroad band light by using Mask Aligner MA-8 (manufactured by SUSS MicroTec AG). After the exposure, the substrate was heated at 110° C. for 2minutes (PEB), and then cooled. Thereafter, patterning was carried outby repeating one-minute puddle development three times using a 2.38%tetramethyl ammonium hydroxide aqueous solution as a developer. Then,the pattern formed on the substrate was post-cured with an oven at 180°C. for 2 hours while purging therein with nitrogen.

In a similar manner, a pattern is formed on a SiN substrate and on a Cusubstrate in place of the silicon substrate.

Similarly, each of the resist compositions 13 and 14 (5 mL) wasdispensed on a silicon substrate, and then the substrate was rotated toapply the resist composition so as to give a film thickness of 20 μm.

Then, pre-bake was carried out on a hot plate at 100° C. for 2 minutes.Subsequently, this substrate was mounted with a mask capable of forming20 μm holes arranged in 1:1 lengthwise and breadthwise, and exposed to abroad band light by using Mask Aligner MA-8 (manufactured by SUSS MicroTec AG). After the exposure, the substrate was heated at 110° C. for 2minutes (PEB), and then cooled. Thereafter, patterning was carried outby repeating 180-seconds spray development three times using isopropylalcohol as a developer. Then, the pattern formed on the substrate waspost-cured with an oven at 180° C. for 2 hours while purging thereinwith nitrogen.

In a similar manner, a pattern is formed on a SiN substrate and on a Cusubstrate in place of the silicon substrate.

Next, each substrate was cut-out so that the shape of the obtained holepattern can be observed. The shape of the hole pattern was observed byusing a scanning electron microscope (SEM). The optimum exposure dose(converted to an exposure dose of 365 nm light) to give an aperturediameter of the hole pattern equal to the mask size of 20 μm is shown inTable 2. The observed shape is also shown in Table 2.

TABLE 2 Pattern Pattern Pattern profile profile profile and exposure andexposure and exposure Resist com- dose (mJ) on dose (mJ) on dose (mJ) onposition silicon substrate SiN substrate Cu substrate Exam- Resist com-Rectangular Forward Forward ple 1 position 1 600 tapered 650 tapered 650Exam- Resist com- Forward Forward Forward ple 2 position 2 tapered 700tapered 750 tapered 750 Exam- Resist com- Forward Forward Forward ple 3position 3 tapered 700 tapered 750 tapered 750 Exam- Resist com-Rectangular Forward Forward ple 4 position 4 400 tapered 450 tapered 450Exam- Resist com- Rectangular Forward Forward ple 5 position 5 600tapered 650 tapered 650 Exam- Resist com- Rectangular Forward Forwardple 6 position 6 400 tapered 450 tapered 450 Exam- Resist com-Rectangular Forward Forward ple 7 position 7 400 tapered 450 tapered 450Exam- Resist com- Rectangular Forward Forward ple 8 position 8 400tapered 450 tapered 450 Exam- Resist com- Rectangular Forward Forwardple 9 position 9 600 tapered 650 tapered 650 Exam- Resist com-Rectangular Forward Forward ple 10 position 10 600 tapered 650 tapered650 Exam- Resist com- Rectangular Forward Forward ple 11 position 11 600tapered 650 tapered 650 Compar- Resist com- Not Not Not ative Ex-position 12 resolved resolved resolved ample 1 Exam- Resist com- ForwardForward Forward ple 12 position 13 tapered 800 tapered 800 tapered 800Exam- Resist com- Forward Forward Forward ple 13 position 14 tapered 800tapered 800 tapered 800

As shown in Table 2, resist compositions 1 to 11, which contain thesilicone skeleton-containing polymer compound of the present invention,could form a pattern having a good profile on any of silicon substrate,SiN substrate, and Cu substrate without remarkable delamination of thepattern by using a 2.38% tetramethyl ammonium hydroxide aqueous solutionas a developer.

On the other hand, resist composition 12, which contains the siliconeskeleton-containing polymer compound (B-2) having no constitutional unitT of the present invention (i.e., a phenol phthalein skeleton or aphenol red skeleton shown by the general formula (2)), could not form apattern by using a 2.38% tetramethyl ammonium hydroxide aqueous solutionas a developer.

Moreover, resist compositions 13 and 14, which contain the siliconeskeleton-containing polymer compound of the present invention, couldform a pattern having a good profile on any of silicon substrate, SiNsubstrate, and Cu substrate without remarkable delamination of thepattern by using isopropyl alcohol as a developer.

III. Production of Photo-Curable Dry Film

For photo-curable dry film, solutions of the siliconeskeleton-containing polymer compounds (A-10) to (A-20) synthesized inSynthesis Examples 14 to 24 were blended with a crosslinking agent, aphotosensitive acid generator, and a basic compound, with thecomposition and the blending ratio shown in Table 1, in the same manneras above except using no additional cyclopentanone. Thereafter, theywere stirred, mixed, dissolved, and then filtered through a 1.0 μmfilter made of Teflon (registered trade mark) for microfiltration toobtain resist compositions 1′ to 11′.

By using a die coater as a film coater and a polyethylene terephthalatefilm (thickness of 38 μm) as a supporting film, resist compositions 1′to 11′ were each applied onto the supporting film so as to give athickness of 50 μm. Then, each was passed through a hot-air circulatingoven (length of 4 m) at 100° C. over 5 minutes to form a photo-curableresin layer on the supporting film. Thereafter, a polyethylene film(thickness of 50 μm) was laminated as a top coat film onto thephoto-curable resin layer by using a laminate roll under pressure of 1MPa to obtain photo-curable dry films 1 to 11.

Meanwhile, the thickness of the photo-curable resin layer was 50 μm. Theexemplary films are shown in Table 3 as Examples.

IV. Exposure and Pattern Formation

The top coat films of photo-curable dry films 1 to 11 obtained asmentioned above was delaminated. Then, the photo-curable resin layer onthe supporting film was brought into close contact with a siliconsubstrate at 100° C. by using a vacuum laminator TEAM-100RF(manufactured by Takatori Corp.) with a vacuum degree in the vacuumchamber of 100 Pa. After the pressure was resumed to normal pressure,the substrate was cooled to 25° C., taken out from the vacuum laminator,and then, the supporting film was delaminated.

After delamination of the supporting film, pre-bake was carried out on ahot plate at 100° C. for 5 minutes. Then, this substrate was mountedwith a mask capable of forming 40 μm holes arranged in 1:1 lengthwiseand breadthwise, and exposed to a broad band light by using Mask AlignerMA-8 (manufactured by SUSS Micro Tec AG). After the exposure, thesubstrate was heated at 130° C. for 5 minutes (PEB), and then cooled.Thereafter, patterning was carried out by repeating one-minute puddledevelopment three times by using a 2.38% tetramethyl ammonium hydroxideaqueous solution as a developer. Then, the obtained pattern waspost-cured by using an oven at 180° C. for 2 hours while purging thereinwith nitrogen.

The photo-curable dry films 1 to 11 thus produced were also laminated toa SiN substrate and on a Cu substrate in place of the silicon substrate,and a pattern was then formed in a similar manner as mentioned above.

Next, each substrate was cut-out so that the shape of the obtained holepattern can be observed. The shape of the hole pattern was observed byusing a scanning electron microscope (SEM). The optimum exposure dose(converted to an exposure dose of 365 nm light) to give an aperturediameter of the hole pattern equal to the mask size of 40 μm is shown inTable 3. The observed shape is also shown in Table 3.

TABLE 3 Pattern Pattern Pattern profile profile profile and exposure andexposure and exposure Photo-curable dose (mJ) on dose (mJ) on dose (mJ)on dry film silicon substrate SiN substrate Cu substrate Exam-Photo-curable Forward Forward Forward ple 14 dry film 1 tapered 750tapered 800 tapered 800 Exam- Photo-curable Forward Forward Forward ple15 dry film 2 tapered 850 tapered 900 tapered 900 Exam- Photo-curableForward Forward Forward ple 16 dry film 3 tapered 850 tapered 900tapered 900 Exam- Photo-curable Forward Forward Forward ple 17 dry film4 tapered 550 tapered 600 tapered 600 Exam- Photo-curable ForwardForward Forward ple 18 dry film 5 tapered 750 tapered 800 tapered 800Exam- Photo-curable Forward Forward Forward ple 19 dry film 6 tapered550 tapered 600 tapered 600 Exam- Photo-curable Forward Forward Forwardple 20 dry film 7 tapered 550 tapered 600 tapered 600 Exam-Photo-curable Forward Forward Forward ple 21 dry film 8 tapered 550tapered 600 tapered 600 Exam- Photo-curable Forward Forward Forward ple22 dry film 9 tapered 750 tapered 800 tapered 800 Exam- Photo-curableForward Forward Forward ple 23 dry film 10 tapered 750 tapered 800tapered 800 Exam- Photo-curable Forward Forward Forward ple 24 dry film11 tapered 750 tapered 800 tapered 800

As shown in Table 3, photo-curable dry film 1 to 11, which uses thephoto-curable resin composition containing the siliconeskeleton-containing polymer compound of the present invention, couldform a pattern having a good profile on any of silicon substrate, SiNsubstrate, and Cu substrate without remarkable delamination of thepattern.

V. Fill-Up Performance

A 6-inch (150 mm) diameter silicon wafer having 200 circular holes eachhaving an aperture diameter of 10 to 100 μm (pitch of 10 μm) and a depthof 10 to 120 μm (pitch of 10 μm) was prepared. Each top coat film ofphoto-curable dry films 1 to 5 was delaminated, and then, thephoto-curable resin layer on the supporting film was brought into closecontact with the substrate at 100° C. by using a vacuum laminatorTEAM-100RF (manufactured by Takatori Corp.) with a vacuum degree in thevacuum chamber of 100 Pa. After the pressure was resumed to normalpressure, the substrate was cooled to 25° C., taken out from the vacuumlaminator, and then, the supporting film was delaminated.

After delamination of the supporting film, pre-bake was carried out on ahot plate at 100° C. for 5 minutes. Then, the substrate was exposed to abroad band light with the exposure dose (365 nm wavelength) shown inTable 4 by using Mask Aligner MA-8 (manufactured by SUSS Micro Tec AG).After the exposure, the substrate was heated at 110° C. for 5 minutes(PEB), and then cooled. Thereafter, one-minute puddle development wasrepeated three times by using a 2.38% tetramethyl ammonium hydroxideaqueous solution as a developer. Then, post-cure was performed by usingan oven at 180° C. for 2 hours while purging therein with nitrogen. Eachof the substrates thus obtained was diced to expose the cross section ofthe circular holes, and the cross section of the circular holes wasobserved by using a scanning electron microscope (SEM) to evaluatewhether or not defects were present. The results are shown in Table 4.

TABLE 4 Photo-curable Exposure dose Observation result of cir- Examplesdry film (mJ) cular hole cross section Example 25 Photo-curable 700 Nodefect dry film 1 Excellent fill-up Example 26 Photo-curable 800 Nodefect dry film 2 Excellent fill-up Example 27 Photo-curable 800 Nodefect dry film 3 Excellent fill-up Example 28 Photo-curable 600 Nodefect dry film 4 Excellent fill-up Example 29 Photo-curable 700 Nodefect dry film 5 Excellent fill-up

As shown in Table 4, all the circular holes of the silicon wafer havingthe photo-curable dry film of the present invention adhered thereto werefilled up without defect, and thus, it could be clarified that it isexcellent in fill-up performance as a top coat to protect electric andelectronic parts.

VI. Electric Characteristics (Dielectric Breakdown Strength)

Each top coat film of photo-curable dry films 1 to 5 with a filmthickness of 50 μm was delaminated, and then, the photo-curable resinlayer on the supporting film was brought into close contact with asubstrate defined in JIS K 6249 at 100° C. The substrate was then cooledto room temperature, and the supporting film was delaminated. Afterdelamination of the supporting film, pre-bake was carried out on a hotplate at 100° C. for 5 minutes. Further, the substrate was exposed to abroad band light with an exposure dose of 1,000 mJ/cm² (365 nmwavelength) by using the above-mentioned mask aligner via a quartzphotomask, heated at 110° C. for 5 minutes (PEB), and then cooled.Thereafter, patterning was carried out by repeating one-minute puddledevelopment three times by using a 2.38% tetramethyl ammonium hydroxideaqueous solution as a developer. Then, post-cure was performed by usingan oven at 180° C. for 2 hours while purging therein with nitrogen toobtain a substrate for measurement of dielectric breakdown strength. Thedielectric breakdown strength was measured in accordance with themeasurement method defined in JIS K 6249. The results are shown in Table5.

VII. Adhesiveness

Each top coat film of photo-curable dry films 1 to 5 with a filmthickness of 50 μm was delaminated, and then, the photo-curable resinlayer on the supporting film was brought into close contact with anuntreated 6-inch (150 mm) silicon wafer at 100° C. by using a vacuumlaminator with a vacuum degree in the vacuum chamber of 100 Pa. Afterthe pressure was resumed to normal pressure, the substrate was cooled to25° C., taken out from the vacuum laminator, and then, the supportingfilm was delaminated. After delamination of the supporting film,pre-bake was carried out on a hot plate at 100° C. for 5 minutes.

Then, the substrate was exposed to a broad band light with an exposuredose of 1,000 mJ/cm² (365 nm wavelength) by using the above-mentionedmask aligner via a quartz photomask, heated at 110° C. for 5 minutes(PEB), and then cooled. Thereafter, post-cure was carried out by usingan oven at 180° C. for 2 hours while purging therein with nitrogen toobtain the wafer having a post-cured film.

The obtained wafer was cut out into a square having a size of 1×1 cm.Then, an aluminum pin with epoxy adhesive was fastened to the cut waferby means of a dedicated jig. Thereafter, the assembly was heated with anoven at 150° C. for 1 hour to bond the aluminum pin to the wafer. Aftercooled to room temperature, initial adhesiveness was evaluated from theresistance force by using a thin-film adhesion strength measurementapparatus (Sebastian Five-A). Herein, the measurement was performed witha measurement rate of 0.2 kg/sec. FIG. 1 is an explanatory view of themethod for measuring adhesiveness. In FIG. 1, reference number 1 denotesa silicon wafer (substrate), 2 denotes a cured film, 3 denotes analuminum pin with adhesive, 4 denotes a support, 5 denotes a grip, and 6denotes tensile direction. The obtained value is an average of 12measurement points, and a larger value indicates a higher adhesionstrength of the cured film to the substrate. Adhesiveness was evaluatedby comparing the obtained values. The results are shown in Table 5.

VIII. Crack Resistance

Each top coat film of photo-curable dry films 1 to 5 with a filmthickness of 50 vim was delaminated, and then, the photo-curable resinlayer on the supporting film was brought into close contact with thesame substrate as used in the fill-up performance test mentioned above,at 100° C. by using the above-mentioned vacuum laminator with a vacuumdegree in the vacuum chamber of 100 Pa. After the pressure was resumedto normal pressure, the substrate was cooled to 25° C., taken out fromthe vacuum laminator, and then, the supporting film was delaminated.

After delamination of the supporting film, pre-bake was carried out on ahot plate at 100° C. for 5 minutes. Then, the substrate was exposed to abroad band light with an exposure dose of 1,000 mJ/cm² (365 nmwavelength) by using the above-mentioned mask aligner via a quartzphotomask. Thereafter, one-minute puddle development was repeated threetimes by using a 2.38% tetramethyl ammonium hydroxide aqueous solutionas a developer. Subsequently, post-cure was carried out by using an ovenat 180° C. for 2 hours while purging therein with nitrogen.

This substrate having the cured film formed thereon was put into athermal cycle tester with a temperature profile of −55° C. to +150° C.as one cycle, and subjected to 1,000 cycles to examine whether or not acrack was formed in the cured film. The results are shown in Table 5.

IX. Resistance to Removing Liquid

Each top coat film of photo-curable dry films 1 to 5 with a filmthickness of 50 μm was delaminated, and then, the photo-curable resinlayer on the supporting film was brought into close contact with anuntreated 6-inch (150 mm) silicon wafer at 100° C. by using theabove-mentioned vacuum laminator with a vacuum degree in the vacuumchamber of 100 Pa. After the pressure was resumed to normal pressure,the substrate was cooled to 25° C., taken out from the vacuum laminator,and then, the supporting film was delaminated.

After delamination of the supporting film, pre-bake was carried out on ahot plate at 100° C. for 5 minutes. Then, the substrate was exposed to abroad band light with an exposure dose of 1,000 mJ/cm² (365 nmwavelength) by using the above-mentioned mask aligner via a quartzphotomask, heated at 110° C. for 5 minutes (PEB), and then cooled.Thereafter, one-minute puddle development was repeated three times byusing a 2.38% tetramethyl ammonium hydroxide aqueous solution as adeveloper. Subsequently, post-cure was carried out by using an oven at180° C. for 2 hours while purging therein with nitrogen to obtain a 15mm×15 mm square pattern cured film.

This substrate was soaked in N-methylpyrrolidone (NMP) at roomtemperature for 1 hour, and then, the changes in appearance and filmthickness were examined to evaluate resistance to the removing liquid.The results are shown in Table 5.

TABLE 5 Electric characteristics Crack resistance Resistance to FilmPhoto-curable Dielectric breakdown Adhesiveness (after thermal removingliquid Example dry film strength (V/μm) (kg/cm²) cycle test) (aftersoaking in NMP) Example Photo-curable 350 450 No crack No change inappearance 25 dry film 1 and film thickness Example Photo-curable 360460 No crack No change in appearance 26 dry film 2 and film thicknessExample Photo-curable 360 500 No crack No change in appearance 27 dryfilm 3 and film thickness Example Photo-curable 350 480 No crack Nochange in appearance 28 dry film 4 and film thickness ExamplePhoto-curable 340 470 No crack No change in appearance 29 dry film 5 andfilm thickness

As shown in Table 5, the cured film obtained by the patterning processusing the photo-curable dry film of the present invention was excellentin all in electric characteristics, adhesiveness, crack resistance, andresistance to removing liquid, as a top coat to protect electric andelectronic parts.

It is to be noted that the present invention is not restricted to theforegoing embodiment. The embodiment is just an exemplification, and anyexamples that have substantially the same feature and demonstrate thesame functions and effects as those in the technical concept describedin claims of the present invention are included in the technical scopeof the present invention.

What is claimed is:
 1. A silicone skeleton-containing polymer compoundcomprising a repeating unit shown by the general formula (1),

wherein R¹ to R⁴ may be the same or different, and represent amonovalent organic group having 1 to 15 carbon atoms and optionallycontaining an oxygen atom; R⁵ and R⁶ may be the same or different, andrepresent a monovalent organic group having 1 to 28 carbon atoms andoptionally containing an oxygen atom; “1” represents an integer of 0 to100; “m” represents an integer of 0 to 100; “n” represents an integer of1 or more; and T represents a divalent organic group shown by thegeneral formula (2),

wherein Q is any of

and the dotted line represents a bond.
 2. The siliconeskeleton-containing polymer compound according to claim 1, wherein thesilicone skeleton-containing polymer compound contains a repeating unitshown by the general formula (3) and has a weight average molecularweight of 3,000 to 500,000,

wherein “a”, “b”, “c”, “d”, “e”, “f”, “g”, and “h” are each 0 or apositive number, and “i” and “j” are each a positive number, providedthat a+b+c+d+e+f+g+h+i+j=1; X is a divalent organic group shown by thegeneral formula (4); Y is a divalent organic group shown by the generalformula (5); W is a divalent organic group shown by the general formula(6); and U is a divalent organic group shown by the general formula (7),

wherein Z represents a divalent organic group selected from any of

the dotted line represents a bond; “o” represents 0 or 1; R⁷ and R⁸ eachrepresent an alkyl group or an alkoxy group having 1 to 4 carbon atoms,and may be the same or different from each other; and “k” is 0, 1, or 2,

wherein V is a divalent organic group selected from any of

the dotted line represents a bond; “p” represents 0 or 1; R⁹ and R¹⁰each represent an alkyl group or alkoxy group having 1 to 4 carbonatoms, and may be the same or different from each other; and “q” is 0,1, or 2,

wherein the dotted line represents a bond; M represents an alkylenegroup having 1 to 12 carbon atoms or a divalent aromatic group; and R¹¹represents a hydrogen atom or a methyl group,

wherein the dotted line represents a bond; and R¹² represents amonovalent carboxyl-containing organic group.
 3. The siliconeskeleton-containing polymer compound according to claim 2, wherein R¹²in the general formula (7) is a monovalent carboxyl-containing organicgroup shown by the general formula (8),

wherein the dotted line represents a bond; R¹³ to R¹⁶ may be the same ordifferent, and represent a hydrogen atom, a halogen atom, a linear,branched, or cyclic alkyl group having 1 to 12 carbon atoms, or anaromatic group; R¹³ and R¹⁵ may be bonded respectively to R¹⁴ and R¹⁶ toform a substituted or unsubstituted ring structure having 1 to 12 carbonatoms; and “r” is any of 1 to
 7. 4. The silicone skeleton-containingpolymer compound according to claim 3, wherein in the general formula(3), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.8,0≤h≤0.5, 0<i≤0.8, and 0<j≤0.5.
 5. The silicone skeleton-containingpolymer compound according to claim 4, wherein in the general formula(3), a=0, b=0, c=0, d=0, e=0, f=0, 0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and0<j≤0.5.
 6. The silicone skeleton-containing polymer compound accordingto claim 3, wherein in the general formula (1) or the general formula(3), “m” is an integer of 1 to 100; R¹ to R⁴ represent an identical ordifferent monovalent hydrocarbon group having 1 to 8 carbon atoms; R⁵represents a phenyl substituent containing a hydroxyl group or an alkoxygroup as shown by the general formula (9); R⁶ may be the same ordifferent from R¹ to R⁴, and represents a monovalent organic grouphaving 1 to 10 carbon atoms and optionally containing an oxygen atom, orR⁶ may be the same or different from R⁵, and represents a phenylsubstituent containing a hydroxyl group or an alkoxy group as shown bythe general formula (9),

wherein “s” is an integer of 0 to 10; and R¹⁷ represents a hydroxylgroup or a linear, branched, or cyclic alkoxy group having 1 to 12carbon atoms.
 7. The silicone skeleton-containing polymer compoundaccording to claim 6, wherein the phenyl substituent shown by thegeneral formula (9) is one group, or two or more groups selected fromthe formula (10),

wherein the line with a wavy line represents a bonding arm.
 8. Thesilicone skeleton-containing polymer compound according to claim 2,wherein in the general formula (3), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3,0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.8, 0≤h≤0.5, 0<i≤0.8, and 0<j≤0.5.
 9. Thesilicone skeleton-containing polymer compound according to claim 8,wherein in the general formula (3), a=0, b=0, c=0, d=0, e=0, f=0,0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and 0<j≤0.5.
 10. The siliconeskeleton-containing polymer compound according to claim 2, wherein inthe general formula (1) or the general formula (3), “m” is an integer of1 to 100; R¹ to R⁴ represent an identical or different monovalenthydrocarbon group having 1 to 8 carbon atoms; R⁵ represents a phenylsubstituent containing a hydroxyl group or an alkoxy group as shown bythe general formula (9); R⁶ may be the same or different from R¹ to R⁴,and represents a monovalent organic group having 1 to 10 carbon atomsand optionally containing an oxygen atom, or R⁶ may be the same ordifferent from R⁵, and represents a phenyl substituent containing ahydroxyl group or an alkoxy group as shown by the general formula (9),

wherein “s” is an integer of 0 to 10; and R¹⁷ represents a hydroxylgroup or a linear, branched, or cyclic alkoxy group having 1 to 12carbon atoms.
 11. The silicone skeleton-containing polymer compoundaccording to claim 10, wherein the phenyl substituent shown by thegeneral formula (9) is one group, or two or more groups selected fromthe formula (10),

wherein the line with a wavy line represents a bonding arm.
 12. Thesilicone skeleton-containing polymer compound according to claim 2,wherein the divalent organic group shown by the general formula (6) is adivalent organic group shown by the general formula (11), and thedivalent organic group shown by the general formula (7) is a divalentorganic group shown by the general formula (12),

wherein the dotted line represents a bond; and “t” represents a positivenumber of 1 to
 12. 13. The silicone skeleton-containing polymer compoundaccording to claim 2, wherein the divalent organic group shown by thegeneral formula (6) is a divalent organic group shown by the generalformula (13), and the divalent organic group shown by the generalformula (7) is a divalent organic group shown by the general formula(14),

wherein the dotted line represents a bond.
 14. The siliconeskeleton-containing polymer compound according to claim 1, wherein inthe general formula (1), “m” is an integer of 1 to 100; R¹ to R⁴represent an identical or different monovalent hydrocarbon group having1 to 8 carbon atoms; R⁵ represents a phenyl substituent containing ahydroxyl group or an alkoxy group as shown by the general formula (9);R⁶ may be the same or different from R¹ to R⁴, and represents amonovalent organic group having 1 to 10 carbon atoms and optionallycontaining an oxygen atom, or R⁶ may be the same or different from R⁵,and represents a phenyl substituent containing a hydroxyl group or analkoxy group as shown by the general formula (9),

wherein “s” is an integer of 0 to 10; and R¹⁷ represents a hydroxylgroup or a linear, branched, or cyclic alkoxy group having 1 to 12carbon atoms.
 15. The silicone skeleton-containing polymer compoundaccording to claim 14, wherein the phenyl substituent shown by thegeneral formula (9) is one group, or two or more groups selected fromthe formula (10),

wherein the line with a wavy line represents a bonding arm.
 16. Achemically amplified negative resist composition comprising: (A) thesilicone skeleton-containing polymer compound according to claim 1, (B)a photosensitive acid generator capable of generating an acid bydecomposition with light having a wavelength of 190 to 500 nm; (C) oneor more crosslinking agents selected from an amino condensate modifiedby formaldehyde or formaldehyde-alcohol, a phenol compound having onaverage two or more methylol groups or alkoxymethylol groups permolecule, a polyhydric phenol compound in which a hydrogen atom of aphenolic hydroxyl group is substituted by a glycidyl group, a polyhydricphenol compound in which a hydrogen atom of a phenolic hydroxyl group issubstituted by a substituent shown by the formula (C-1), and a compoundhaving two or more nitrogen atoms bonded to a glycidyl group as shown bythe formula (C-2),

wherein the dotted line represents a bond; R_(c) represents a linear,branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1or 2; (D) a solvent; and (E) a basic compound.
 17. A photo-curable dryfilm comprising a supporting film, a top coat film, and a photo-curableresin layer having a film thickness of 10 to 100 μm, the photo-curableresin layer being sandwiched between the supporting film and the topcoat film, wherein the photo-curable resin layer is formed of thechemically amplified negative resist composition according to claim 16.18. A patterning process comprising: (i) separating the top coat filmfrom the photo-curable dry film according to claim 17 and bringing anexposed photo-curable resin layer into close contact with a substrate;(ii) exposing the photo-curable resin layer to a high energy beam havinga wavelength of 190 to 500 nm or an electron beam via a photomask eitherthrough the supporting film or in a peeled-off state of the supportingfilm; (iii) subjecting to a heat treatment after the exposure; and (iv)subjecting to development by using an alkaline aqueous solution or anorganic solvent as a developer.
 19. The patterning process according toclaim 18, wherein the substrate includes a trench and/or a hole eachhaving an aperture width of 10 to 100 μm and a depth of 10 to 120 μm.20. A method for producing a photo-curable dry film, comprising: (I)continuously applying the chemically amplified negative resistcomposition according to claim 16 onto a supporting film to form aphoto-curable resin layer, (II) continuously drying the photo-curableresin layer, and further (III) laminating a top coat film onto thephoto-curable resin layer.
 21. A patterning process comprising: (1)applying the chemically amplified negative resist composition accordingto claim 16 onto a substrate to form a photosensitive material film; (2)exposing the photosensitive material film to a high energy beam having awavelength of 190 to 500 nm or an electron beam via a photomask after aheat treatment; and (3) subjecting to development by using an alkalineaqueous solution or an organic solvent as a developer after a heattreatment.
 22. The patterning process according to claim 21, furthercomprising post-curing a patterned film formed by the development at 100to 250° C. after the development.
 23. A substrate that is protected by afilm obtained by curing a pattern formed by the patterning processaccording to claim
 21. 24. A semiconductor apparatus comprising a filmobtained by curing a pattern formed by the patterning process accordingto claim
 21. 25. A layered product comprising a substrate including atrench and/or a hole each having an aperture width of 10 to 100 μm and adepth of 10 to 120 μm, and a photo-curable resin layer laminated on thesubstrate, wherein the photo-curable resin layer has a film thickness of10 to 100 μm and is formed of the chemically amplified negative resistcomposition according to claim 16.